Production of Alpha, Omega-Diols

ABSTRACT

Disclosed herein are processes for preparing an α,ω-C n -diol, wherein n is 5 or greater, from a feedstock comprising a C n  oxygenate. In one embodiment, the process comprises contacting the feedstock with hydrogen gas in the presence of a catalyst comprising Pt, Cu, Ni, Pd, Pt, Rh, Ir, Ru, or Fe on a WO 3  or WO x  support. In one embodiment, the process comprises contacting the feedstock with hydrogen in the presence of a catalyst comprising a metal M1 and a metal M2 or an oxide of M2, and optionally a support. In one embodiment, M1 is Pd, Pt, or Ir; and M2 is Mo, W, V, Mn, Re, Zr, Ni, Cu, Zn, Cr, Ge, Sn, Ti, Au, or Co. The C n  oxygenate may be obtained from a biorenewable resource.

This application claims priority under 35 U.S.C. §119(e) from, andclaims the benefit of, U.S. Provisional Application No. 61/639,404 filedApr. 27, 2012, which is by this reference incorporated in its entiretyas a part hereof for all purposes.

FIELD OF DISCLOSURE

The present invention relates to processes for preparing alpha,omega-diols (“α,ω-diols”). More particularly, the present inventionrelates to processes for preparing α,ω-diols by selectivehydrodeoxygenation of oxygenated compounds which can be derived fromcarbohydrates or biologic sources.

BACKGROUND

The α,ω-diols such as 1,5-pentanediol and 1,6-hexanediol are useful aschemical intermediates for the production of agrichemicals,pharmaceuticals, and polymers. For example, α,ω-diols can be used asplasticizers and as comonomers in polyesters and polyether-urethanes. Ithas become increasingly desirable to obtain industrial chemicals such asα,ω-diols, or their precursors, from materials that are not onlyinexpensive but also benign in the environment. Of particular interestare materials which can be obtained from renewable sources, that is,materials that are produced by a biological activity such as planting,farming, or harvesting. As used herein, the terms “renewable” and“biosourced” can be used interchangeably.

Biomass sources for such materials are becoming more attractiveeconomically versus petroleum-based ones. Although the convergent andselective synthesis of C₅ and C₆ carbocyclic intermediates from biomassis difficult because of the high degree of oxygenation of manycomponents of biomass, use of such biomass-derived intermediates asfeedstocks would offer new routes to industrially useful chemicals.

1,6-Hexanediol is a useful intermediate in the industrial preparation ofnylon 66. 1,6-Hexanediol can be converted by known methods to1,6-hexamethylene diamine, a starting component in nylon production.1,6-Hexanediol is typically prepared from the hydrogenation of adipicacid or its esters or the hydrogenation of caprolactone or itsoligomers. For example, in WO 2011/149339, deVries J-G, et al describe aprocess for the preparation of caprolactone, caprolactam,2,5-tetrahydrofuran-dimethanol, 1,6-hexanediol or 1,2,6-hexanetriol from5-hydroxymethyl-2-furfuraldehyde and teach that 1,2,6-hexanetriol may behydrogenated to 1,6-hexanediol using a catalyst based on palladium,nickel, rhodium, ruthenium, copper and chromium or mixtures thereof.Further, the catalysts may be doped with one or more other elements,such as rhenium.

JP 2003-183200 teaches a method for preparation of2,5-diethyl-1,6-hexanediol from tetrahydropyran derivatives, e.g.2,5-diethyltetrahydropyran-2-methanol, comprising hydrogenation of thestarting material in the presence of a metal catalyst carried on anacidic support, notably 5% Pt/Al₂O₃ and 5% Pt/SiO₂—Al₂O₃ at 200-240° C.Yields ranged from 40 to 61%.

There is an existing need for processes to make α,ω-diols, especially C₅and C₆ α,ω-diols, and synthetic intermediates useful in the productionof α,ω-diols, from renewable biosources. There is an existing need forprocesses to produce 1,5-pentanediol, 1,6-hexanediol, and otherα,ω-diols at high yield and high selectivity from biomass-derivedstarting materials, including 1,2,6-hexanetriol,tetrahydrofuran-2,5-dimethanol, and 2-hydroxymethyltetrahydropyran.

SUMMARY

In one embodiment, a process for preparing an α,ω-C_(n)-diol isprovided, the process comprising the steps:

(a) providing a feedstock comprising a C_(n) oxygenate;

(b) contacting the feedstock with hydrogen gas, in the presence of acatalyst at a temperature and for a time sufficient to form a productmixture comprising α,ω-C_(n)-diol; wherein n is 5 or greater; andwherein the catalyst comprises Pt, Cu, Ni, Pd, Rh, Ir, Ru, or Fe on aWO₃ or WO_(x) support.

In another embodiment, a process for preparing an α,ω-C_(n)-diol isprovided, the process comprising the steps:

(a) providing a feedstock comprising a C_(n) oxygenate;

(b) contacting the feedstock with hydrogen gas, in the presence of acatalyst at a temperature and for a time sufficient to form a productmixture comprising an α,ω-C_(n)-diol; wherein n is 5 or greater;

and wherein the catalyst comprises a metal M1 and a metal M2 or an oxideof M2, and optionally a support, wherein:

M1 is Pd, Pt, or Ir; and M2 is Mo, W, V, Mn, Re, Zr, Ni, Cu, Zn, Cr, Ge,Sn, Ti, Au, or Co; or

M1 is Rh and M2 is Mo, W, V, Mn, Ni, Cu, Zn, Cr, Ge, Sn, Ti, Au, or Zr;or

M1 is Ag, Au or Co; and M2 is Re, Mo, or W; or

M1 is Cu, Pd, Fe, or Ni; and M2 is Re, Mo, Cu, Zn, Cr, Ge, Sn, or W; or

M1 is Ag, Pt, Cu, or Au, and M2 is Ni, Fe, Sn, Ge, or Ir; or

M1 is Co and M2 is Fe; or

M1 is Ni and M2 is Co or Fe; or

M1 is Mn and M2 is Cr.

DETAILED DESCRIPTION

As used herein, where the indefinite article “a” or “an” is used withrespect to a statement or description of the presence of a step in aprocess disclosed herein, it is to be understood, unless the statementor description explicitly provides to the contrary, that the use of suchindefinite article does not limit the presence of the step in theprocess to one in number.

As used herein, when an amount, concentration, or other value orparameter is given as either a range, preferred range, or a list ofupper preferable values and lower preferable values, this is to beunderstood as specifically disclosing all ranges formed from any pair ofany upper range limit or preferred value and any lower range limit orpreferred value, regardless of whether ranges are separately disclosed.Where a range of numerical values is recited herein, unless otherwisestated, the range is intended to include the endpoints thereof, and allintegers and fractions within the range. It is not intended that thescope of the invention be limited to the specific values recited whendefining a range.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains” or “containing,” or any othervariation thereof, are intended to cover a non-exclusive inclusion. Forexample, a composition, a mixture, process, method, article, orapparatus that comprises a list of elements is not necessarily limitedto only those elements but may include other elements not expresslylisted or inherent to such composition, mixture, process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

As used herein, the term “about” modifying the quantity of an ingredientor reactant employed refers to variation in the numerical quantity thatcan occur, for example, through typical measuring and liquid handlingprocedures used for making concentrates or use solutions in the realworld; through inadvertent error in these procedures; throughdifferences in the manufacture, source, or purity of the ingredientsemployed to make the compositions or carry out the methods; and thelike. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities. The term “about” maymean within 10% of the reported numerical value, preferably within 5% ofthe reported numerical value.

As used herein, the term “organic compound” means a carbon-containingcompound with the following exceptions: binary compounds as the carbonoxides, carbides, carbon disulfide, etc.; ternary compounds such asmetallic cyanides, metallic carbonyls, phosgene, carbonylsulfide; andmetallic carbonates such as calcium carbonate and sodium carbonate.

As used herein, the term “oxygenate” means an organic compoundcontaining at least one oxygen atom. As used herein, the term “C_(e)oxygenate” means an oxygenate containing n carbon atoms and,analogously, the term “C_(n) diol” denotes a diol containing n carbonatoms.

As used herein, the term “biomass” refers to any cellulosic orlignocellulosic material and includes materials comprisinghemicellulose, and optionally further comprising lignin, starch,oligosaccharides and/or monosaccharides.

As used herein, the term “lignocellulosic” means comprising both ligninand cellulose. Lignocellulosic material may also comprise hemicellulose.In some embodiments, lignocellulosic material contains glucan and xylan.

As used herein, the term “hemicellulose” means a non-cellulosicpolysaccharide found in lignocellulosic biomass. Hemicellulose is abranched heteropolymer consisting of different sugar monomers. Ittypically comprises from 500 to 3000 sugar monomeric units.

As used herein, the term “lignin” refers to a complex high molecularweight polymer that can comprise guaiacyl units, as in softwood lignin,or a mixture of guaiacyl and syringyl units, as in hardwood lignin.

As uses herein, the term “starch” refers to a carbohydrate consisting ofa large number of glucose units joined by glycosidic bonds. Starch, alsoknown as amylum, typically contains amylose and amylopectin.

As used herein, the term “sugar” includes monosaccharides,disaccharides, and oligosaccharides. Monosaccharides, or “simplesugars,” are aldehyde or ketone derivatives of straight-chainpolyhydroxy alcohols containing at least three carbon atoms. A pentoseis a monosaccharide having five carbon atoms; examples include xylose,arabinose, lyxose, and ribose. A hexose is a monosaccharide having sixcarbon atoms; examples include glucose and fructose. Disaccharidemolecules consist of two covalently linked monosaccharide units;examples include sucrose, lactose, and maltose. As used herein,“oligosaccharide” molecules consist of about 3 to about 20 covalentlylinked monosaccharide units. Unless indicated otherwise herein, allreferences to specific sugars are intended to include theD-stereoisomer, the L-stereoisomer, and mixtures of the stereoisomers.

As used herein, the term “C_(n) sugar” includes monosaccharides having ncarbon atoms; disaccharides comprising monosaccharide units having ncarbon atoms; and oligosaccharides comprising monosaccharide unitshaving n carbon atoms. Thus, the term “C₅ sugar” includes pentoses,disaccharides comprising pentose units, and oligosaccharides comprisingpentose units; the term “C₆ sugar” includes hexoses, disaccharidescomprising hexose units, and oligosaccharides comprising hexose units.

As used herein, the term “C_(n) sugar alcohol” refers to compoundsproduced from C_(n) sugars by reduction of the carbonyl group to aprimary or secondary hydroxyl group. Sugar alcohols having the generalformula H(HCHO)_(x+1)H, are derived from sugars having the generalformula H(HCHO)_(x)HCO. Monosaccharides and disaccharides can be used toform sugar alcohols, though the disaccharides are not fullyhydrogenated. Three examples of sugar alcohols are xylitol (C₅),sorbitol (C₆), and mannitol (C₆).

As used herein, the abbreviation “16HD” refers to 1,6-hexanediol. Thechemical structure of 1,6-hexanediol is represented by Formula (I).

As used herein, the abbreviation “15PD” refers to 1,5-pentanediol. Thechemical structure of 1,5-pentanediol is represented by Formula (II).

As used herein, the abbreviation “126HT” refers to 1,2,6-hexanetriol andincludes a racemic mixture of isomers. The chemical structure of1,2,6-hexanetriol is represented by Formula (III).

As used herein, the abbreviation “125PT” refers to 1,2,5-pentanetrioland includes a racemic mixture of isomers. The chemical structure of1,2,5-pentanetriol is represented by Formula (IV).

As used herein, the abbreviation “Tetraol” refers to1,2,5,6-tetrahydroxyhexane, also known as 3,4-dideoxyhexitol, andincludes a mixture of stereoisomers. The chemical structure of1,2,5,6-tetrahydroxyhexane is represented by Formula (V).

As used herein, the abbreviation “Pentaol” refers to1,2,3,5,6-hexanepentaol and includes a racemic mixture of isomers. Thechemical structure of 1,2,3,5,6-hexanepentaol is represented by Formula(VI).

As used herein, the abbreviation “THFdM” refers totetrahydro-2,5-furandimethanol (also known astetrahydrofuran-2,5-dimethanol or 2,5-tetrahydrofurandimethanol, or2,5-bis[hydroxymethyl]tetrahydrofuran) and includes a mixture ofstereoisomers (cis and racemic trans isomers). The chemical structure oftetrahydro-2,5-furandimethanol is represented by Formula (VII).

The chemical structure of 2,5-dihydrofuran-2,5-dimethanol is representedby Formula (VIII).

As used herein, the abbreviation “FdM” refers to 2,5-furandimethanol,also known as 2,5-bis(hydroxymethyl)furan. The chemical structure of2,5-furandimethanol is represented by Formula (IX).

The chemical structure of furfural, also known as furan-2-carbaldehydeor 2-furaldehyde, is represented by Formula (X).

The chemical structure of hydroxymethylfurfural, also known as5-(hydroxymethyl)-2-furaldehyde, is represented by Formula (XI).

The chemical structure of furfuryl alcohol, also known as2-furanmethanol, is represented by Formula (XII).

The chemical structure of tetrahydrofurfuryl alcohol, also known astetrahydro-2-furanmethanol, is represented by Formula (XIII).

As used herein, the abbreviation “THPM” refers totetrahydro-2H-pyran-2-methanol, also known as2-hydroxymethyltetrahydropyran, and includes a racemic mixture ofisomers. The chemical structure of tetrahydro-2H-pyran-2-methanol isrepresented by Formula (XIV).

As used herein, the abbreviation “HOTHPM” refers to2-hydroxymethyl-5-hydroxytetrahydro-2H-pyran, also known as5-hydroxy-2H-tetrahydropyran-2 methanol or1,5-anhydro-3,4-dideoxyhexitol, and includes a mixture of stereoisomers.The chemical structure of 2-hydroxymethyl-5-hydroxytetrahydro-2H-pyranis represented by Formula (XV).

The chemical structure of 3,4-dihydro-2H-pyran-2-carbaldehyde, alsoknown as 3,4-dihydro-2H-pyran-2-carboxaldehyde,2-formyl-3,4-dihydro-2H-pyran, or “acrolein dimer”, is represented byFormula (XVI).

The chemical structure of levoglucosan, also known as1,6-anhydro-β-glucopyranose, is represented by Formula (XVII).

As used herein, the abbreviations “Lgone” and “LGone” refer tolevoglucosenone, also known as1,6-anhydro-3,4-dideoxy-β-D-pyranosen-2-one. The chemical structure oflevoglucosenone is represented by Formula (XVIII).

The chemical structure of 1,6-anhydro-3,4-dideoxy-β-D-pyranose-2-one isrepresented by Formula (XIX).

The chemical structure of levoglucosenol, also known as1,6-anhydro-3,4-dideoxy-β-erythro-hex-3-enopyranose, is represented byFormula (XX).

As used herein, the abbreviations “Lgol” and “LGol” refer tolevoglucosanol, also known as 1,6-anhydro-3,4-dideoxyhexopyranose, andinclude a mixture of the threo and erythro stereoisomers. The chemicalstructure of 1,6-anhydro-3,4-dideoxyhexopyranose is represented byFormula (XXI).

As used herein, the abbreviation “ISOS” refers to isosorbide, also knownas 1,4:3,6-dianhydrosorbitol or 1,4-dianhydrosorbitol. The chemicalstructure of isosorbide is represented by Formula (XXII).

The chemical structure of sorbitol, also known ashexane-1,2,3,4,5,6-hexol, is represented by Formula (XXIII).

The chemical structure of glucose, also known as dextrose or2,3,4,5,6-pentahydroxyhexanal, is represented by Formula (XXIV).

The chemical structure of fructose, also known as levulose, isrepresented by Formula (XXV).

The chemical structure of xylitol, also known aspentane-1,2,3,4,5-pentol, is represented by Formula (XXVI).

In one embodiment, a process is provided for preparing an α,ω-C_(n)-diolvia selective hydrodeoxygenation, the process comprising the steps:

(a) providing a feedstock comprising a C_(n) oxygenate;

(b) contacting the feedstock with hydrogen gas, in the presence of acatalyst at a temperature and for a time sufficient to form a productmixture comprising an α,ω-C_(n)-diol; wherein n is 5 or greater;

and wherein the catalyst comprises Pt, Cu, Ni, Pd, Rh, Ir, Ru, or Fe ona WO₃ support.

In another embodiment, a process is provided for preparing anα,ω-C_(n)-diol via selective hydrodeoxygenation, the process comprisingthe steps:

(a) providing a feedstock comprising a C_(n) oxygenate;

(b) contacting the feedstock with hydrogen gas, in the presence of acatalyst at a temperature and for a time sufficient to form a productmixture comprising an α,ω-C_(n)-diol; wherein n is 5 or greater;

and wherein the catalyst comprises a metal M1 and a metal M2 or an oxideof M2, and optionally a support, wherein:

M1 is Pd, Pt, or Ir; and M2 is Mo, W, V, Mn, Re, Zr, Ni, Cu, Zn, Cr, Ge,Sn, Ti, Au, or Co; or

M1 is Rh and M2 is Mo, W, V, Mn, Ni, Cu, Zn, Cr, Ge, Sn, Ti, Au, or Zr;or

M1 is Ag, Au or Co; and M2 is Re, Mo, or W; or

M1 is Cu, Pd, Fe, or Ni; and M2 is Re, Mo, Cu, Zn, Cr, Ge, Sn, or W; or

M1 is Ag, Pt, Cu, or Au, and M2 is Ni, Fe, Sn, Ge, or Ir; or

M1 is Co and M2 is Fe; or

M1 is Ni and M2 is Co or Fe; or

M1 is Mn and M2 is Cr.

In one embodiment, n=5 or 6. In one embodiment, n=5, and theα,ω-C_(n)-diol is 1,5-pentanediol. In one embodiment, n=6, and theα,ω-C_(n)-diol is 1,6-hexanediol. In one embodiment, n=7, and theα,ω-C_(n)-diol is 1,7-heptanediol. In one embodiment, n=8, and theα,ω-C_(n)-diol is 1,8-octanediol.

Examples of C_(n) oxygenates that are suitable for use in the presentprocesses include 1,2,6-hexanetriol; 1,2,5-pentanetriol;2H-tetrahydropyran-2-methanol; tetrahydrofuran-2,5-dimethanol;furan-2,5-dimethanol; 2,5 dihydrofuran-2,5-dimethanol; levoglucosenone;levoglucosan; levoglucosenol;1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one; isosorbide;hydroxymethylfurfural; sorbitol; glucose; fructose; xylitol;3,4-dihydro-2H-pyran-2-carbaldehyde; 1,2,5,6-hexanetetraol;1,2,3,5,6-hexanepentanol; 1,5-anhydro-3,4-dideoxy-hexitol;5-hydroxy-2H-tetrahydropyran-2 methanol; furfural; furfuryl alcohol;tetrahydrofurfuryl alcohol; pentoses; dimers containing pentose;oligomers containing pentose; hexoses; dimers containing hexose;oligomers containing hexose; condensation products from the reaction of5-(hydroxymethyl)-2-furfural (“HMF”) with ketones and/or aldehydes, andcondensation products from the reaction of furfural with ketones and/oraldehydes. The feedstock may comprise one or more Cn oxygenates.

In one embodiment, the C_(n) oxygenate comprises 1,2,6-hexanetriol;2H-tetrahydropyran-2-methanol; tetrahydrofuran-2,5-dimethanol;levoglucosenone; 3,4-dihydro-2H-pyran-2-carbaldehyde, or mixturesthereof. These C_(n) oxygenates are useful for preparation of reactionmixtures comprising 1,6-hexanediol by the processes disclosed herein. Inone embodiment, the C_(n) oxygenate comprises 1,2,6-hexanetriol.

In one embodiment, the C_(n) oxygenate comprises 1,2,5-pentanetriol;furfural; furfuryl alcohol; tetrahydrofurfuryl alcohol; xylitol; ormixtures thereof. These C_(n) oxygenates are useful for preparation ofproduct mixtures comprising 1,5-hexanediol by the processes disclosedherein.

Examples of suitable pentoses include without limitation xylose,arabinose, lyxose, xylitol, and ribose. Examples of suitable hexosesinclude without limitation glucose, mannose, fructose, and galactose.Examples of condensation products from the reaction of furfural or5-(hydroxymethyl)-2-furfural with ketones and/or aldehydes are describedin Synthesis (2008), (7), 1023-1028 (e.g., CAS Reg. No. 1040375-91-4 andCAS Reg. No. 886-77-1); and in ChemSusChem (2010), 3(10), 1158-1161, inwhich subjecting furfural and 5-(hydroxymethyl)-2-furfural to aldolcondensation produced molecules having 8 to 15 carbon atoms.

Suitable C_(n) oxygenates can be derived from biorenewable resourcesincluding biomass. Biomass may be derived from a single source, orbiomass can comprise a mixture derived from more than one source; forexample, biomass could comprise a mixture of corn cobs and corn stover,or a mixture of grass and leaves. Biomass includes, but is not limitedto, bioenergy crops, agricultural residues, municipal solid waste,industrial solid waste, sludge from paper manufacture, yard waste, woodand forestry waste or a combination thereof. Examples of biomassinclude, but are not limited to, corn grain, corn cobs, crop residuessuch as corn husks, corn stover, grasses, wheat, wheat straw, barley,barley straw, hay, rice straw, switchgrass, waste paper, sugar canebagasse, sorghum, soy, components obtained from milling of grains,trees, branches, roots, leaves, wood chips, sawdust, shrubs and bushes,vegetables, fruits, flowers, and animal manure or a combination thereof.Biomass that is useful for the invention may include biomass that has arelatively high carbohydrate value, is relatively dense, and/or isrelatively easy to collect, transport, store and/or handle. In oneembodiment, the C_(n) oxygenate is ultimately derived from corn cobs,sugar cane bagasse, switchgrass, wheat straw, sawdust and other woodwaste, and lignocellulosic feedstocks.

A biorenewable resource such as biomass can be pyrolyzed under hightemperature conditions in the presence of an acid catalyst to provideuseful chemical intermediates. For example, pyrolysis of wood, starch,glucose or cellulose can produce levoglucosenone by known andconventional methods (see, for example, Ponder (Applied Biochemistry andBiotechnology, Vol 24/25, 41-41 (1990)) or Shafizadeh (CarbohydrateResearch, 71, 169-191 (1979)).

Glycerol can be obtained from a biorenewable resource, for example fromhydrolysis of vegetable and animal fats and oils (that is,triacylglycerides comprising ester functionality resulting from thecombination of glycerol with C₁₂ or greater fatty acids).1,2,6-Hexanetriol can be obtained from materials such as glucose,cellulose or glycerol derived from a biorenewable resource. For example,1,2,6-hexanetriol can be obtained by a process comprising the steps ofcontacting glycerol with a catalyst to prepare acrolein, heatingacrolein (optionally in the presence of a catalyst) to prepare2-formyl-3,4-dihydro-2H-pyran, contacting 2-formyl-3,4-dihydro-2H-pyranwith water to prepare 2-hydroxyadipic aldehyde and contacting2-hydroxyadipic aldehyde with hydrogen and a catalyst to produce aproduct mixture comprising 1,2,6-hexanetriol. See, for example, U.S.Pat. No. 2,768,213, German Patent No. 4238493, and L. Ott, et al. inGreen Chem., 2006, 8, 214-220.

The catalysts utilized in the processes described herein can besynthesized by any conventional method for preparing catalysts, forexample, deposition of metal salts from aqueous or organic solventsolutions via impregnation or incipient wetness, precipitation of an M1component and/or an M2 component, or solid state synthesis. Preparationmay comprise drying catalyst materials under elevated temperatures from30-250° C., preferably 50-150° C.; calcination by heating in thepresence of air at temperatures from 250-800° C., preferably 300-450°C.; and reduction in the presence of hydrogen at 100-400° C., preferably200-300° C., or reduction with alternative reducing agents such ashydrazine, formic acid or ammonium formate. The above techniques may beutilized with powdered or formed particulate catalyst materials preparedby tableting, extrusion or other techniques common for catalystsynthesis. Where powdered catalysts materials are utilized, it will beappreciated that the catalyst support or the resulting catalyst materialmay be sieved to a desired particle size and that the particle size maybe optimized to enhance catalyst performance.

In one embodiment of the present invention, the catalyst comprises Pt,Cu, Ni, Pd, Rh, Ir, Ru, or Fe on a WO₃ or WOx support. The metal can bederived from any appropriate metal compound; examples include but arenot limited to: rhodium (III) chloride hydrate, tetraammineplatinum (II)nitrate, ruthenium (III) chloride hydrate, copper (II) nitrate hydrate,palladium nitrate, nickel (II) chloride hexahydrate, iridium (IV)chloride hydrate, and iron (III) nitrate nonahydrate. The WOx support isconsidered to contain partially reduced tungsten trioxide, with theoxidation state of some of the tungsten being less than (VI) but morethan (I).

The loading of M1 may be 0.1-50% but preferably 0.5-5% by weight, basedon the weight of the prepared catalyst (i.e., including the WO₃ orWO_(x) support). The M1/WO₃ catalysts can be prepared, for example, bygrinding and sieving the WO₃ support material as desired andimpregnating into the support via incipient wetness the M1-containingcompound dissolved in a minimum of water, followed by drying (e.g., invacuum at 110° C. for overnight) and then calcining in air at 300-500°C. for several (e.g., 3 to 5) hours. The M1/WOx catalyst can beprepared, for example, by adding the M1-containing compound to anaqueous solution of ammonium tungsten oxide hydrate, followed by dryingthe resulting solid and then calcining it in air, as described in theExperimental section.

In another embodiment, the catalyst comprises a metal M1 and a metal M2or an oxide of M2, and optionally a support, wherein:

M1 is Pd, Pt, or Ir; and M2 is Mo, W, V, Mn, Re, Zr, Ni, Cu, Zn, Cr, Ge,Sn, Ti, Au, or Co; or

M1 is Rh and M2 is Mo, W, V, Mn, Ni, Cu, Zn, Cr, Ge, Sn, Ti, Au, or Zr;or

M1 is Ag, Au or Co; and M2 is Re, Mo, or W;

M1 is Cu, Pd, Fe, or Ni; and M2 is Re, Mo, Cu, Zn, Cr, Ge, Sn, or W; or

M1 is Ag, Pt, Cu, or Au, and M2 is Ni, Fe, Sn, Ge, or Ir; or

M1 is Co and M2 is Fe; or

M1 is Ni and M2 is Co or Fe; or

M1 is Mn and M2 is Cr.

In one embodiment, the catalyst comprises metals M1 and M2, andoptionally a support, wherein M1 is Pd, Pt, or Ir; and M2 is Mo, W, Mn,Re, Zr, Ni, Cu, Zn, Cr, Ti, Au, or Co; or

M1 is Rh and M2 is Mo, W, Mn, Ni, Cu, Zn, Cr, Ti, Au, or Zr; or

M1 is Ag, Au or Co; and M2 is Re, Mo, or W; or

M1 is Cu, Pd, Fe, or Ni; and M2 is Re, Mo, Cu, Zn, Cr, or W; or

M1 is Ag, Pt, Cu, or Au, and M2 is Ni, Fe, or Ir.

In one embodiment, the catalyst comprises metals M1 and M2, andoptionally a support, wherein M1 is Pd, Pt, or Ir; and M2 is Mo, W, V,Mn, Re, Zr, Ni, Cu, Zn, Cr, Ge, Sn, Ti, Au, or Co.

In one embodiment, the catalyst comprises metals M1 and M2, andoptionally a support, wherein M1 is Cu, Pd, Fe, or Ni; and M2 is Re, Mo,Cu, Zn, Cr, Ge, Sn, or W.

In one embodiment, the catalyst comprises metals M1 and M2, andoptionally a support, wherein M1 is Pt and M2 is W; or M1 is Ni and M2is W; or M1 is Cu and M2 is W; or M1 is Cu and M2 is Fe. In oneembodiment, M1 is Pt and M2 is W. In one embodiment, M1 is Ni and M2 isW. In one embodiment, M1 is Cu and M2 is W. In one embodiment, M1 is Cuand M2 is Fe.

The M1 and M2 components of the catalysts may be derived from anyappropriate metal compound. Examples include but are not limited to:rhodium (III) chloride hydrate, copper (II) nitrate hydrate, nickel (II)chloride hexahydrate, iridium (IV) chloride hydrate, iron (III) nitratenonahydrate, tetraammineplatinum (II) nitrate, platinum chloride,hexachloroplatinic acid, tetrachloroplatinic acid, palladium chloride,palladium nitrate, palladium acetate, iridium trichloride, ammoniumperrhenate, ammonium tungsten oxide hydrate, ammonium molybdate hydrate,manganese (II) nitrate hydrate, and ammonium vanadium oxide.

The loading of M1 may be 0.1-50% but preferably 0.5-5% by weight, basedon the weight of the prepared catalyst (i.e., including the catalystsupport where present). The loading of M2 may be 0.1-99.9%, preferably2-10%. Preferably the molar ratio of M1 to M2 in catalysts containingboth M1 and M2 is in the range of 1:0.5 to 1:5. Optionally, M2 may beincorporated into the catalyst support or serve as the catalyst support,e.g. Pt supported on tungsten oxide or molybdenum oxide. Regarding thecatalyst, all percentages are interpreted as weight percent relative tothe weight of the prepared catalyst.

In some embodiments, it is useful to utilize a catalyst which comprisesa support to enhance the stability and economic feasibility of theprocess. Examples of useful supports include WO₃, SiO₂, Al₂O₃, carbon,SiC, TiO₂, ZrO₂, SiO₂—Al₂O₃, clays such as montmorillonite, SiO₂—TiO₂,tungstated ZrO₂, V₂O₅, MoO₃, and zeolites such as H-Y, FAU (H-Y or USY),BEA (H-Beta), MFI (H-ZSM5), MEL (H-ZSM11) and MOR (H-Mordenite).Typically, tungstated ZrO₂ can comprise up to about 19 wt % Was WO₃ onZrO₂, see for example S. Kuba et al in Journal of Catalysis 216 (2003),p. 353-361. In one embodiment, the catalyst further comprises a supportcomprising WO₃, SiO₂, Al₂O₃, carbon, TiO₂, ZrO₂, SiO₂—Al₂O₃,montmorillonite, SiO₂—TiO₂, tungstated ZrO₂, H-Y zeolites, V₂O₅, MoO₃,or mixtures thereof. In one embodiment, the support comprises TiO₂, azeolite, or mixtures thereof. In one embodiment, the support comprisesTiO₂, a zeolite, or mixtures thereof, and M1 is Pt and M2 is W. In otherembodiments, it may be desirable to not have a support.

In some embodiments, the catalyst is mixed with an additive comprisingWO₃, SiO₂, Al₂O₃, carbon, TiO₂, ZrO₂, SiO₂—Al₂O₃, montmorillonite,SiO₂—TiO₂, tungstated ZrO₂, H-Y zeolites, V₂O₅, MoO₃, or mixturesthereof. If the catalyst comprises a support, the support can be thesame or different from the additive. As used herein, the term “support”means a material which is a component of the catalyst (in the caseswhere the optional support is present in the catalyst) and is used aspart of catalyst preparation to anchor the metals M1 and M2, providing asurface for metals M1 and M2 to associate with. As used herein, the term“additive” means a material which can increase catalyst activity throughits physical presence in combination with the catalyst and reactantsunder appropriate reaction conditions. Useful ratios of additive tocatalyst are from 1:10 to 10:1 on a weight basis, for example 2:1 to1:2, or about 1:1, although ratios outside these ranges can also beused. The additive can be added to the reactor together with thecatalyst, or the catalyst and the additive may be added sequentially tothe reactor. The additive, or a mixture of additive and catalyst, can bein any physical form typical for the material, including but not limitedto powdered (also known as “fluidized”) forms with 0.01-150 μm particlesize, formed tablets, extrudates, spheres, engineered particles havinguniform 0.5-10 mm size, or combinations of two or more of the above.

In some embodiments, wherein the optional support is present in thecatalyst and comprises WO₃, SiO₂, Al₂O₃, carbon, TiO₂, ZrO₂, SiO₂—Al₂O₃,montmorillonite, SiO₂—TiO₂, tungstated ZrO₂, zeolites, V₂O₅, MoO₃, ormixtures thereof, the process step (b) further comprises the presence ofan additive comprising WO₃, SiO₂, Al₂O₃, carbon, TiO₂, ZrO₂, SiO₂—Al₂O₃,montmorillonite, SiO₂—TiO₂, tungstated ZrO₂, zeolites, V₂O₅, MoO₃, ormixtures thereof. In some embodiments, the optional support is presentin the catalyst and step (b) further comprises adding an additivecomprising WO₃, SiO₂, Al₂O₃, carbon, TiO₂, ZrO₂, SiO₂—Al₂O₃,montmorillonite, SiO₂—TiO₂, tungstated ZrO₂, zeolites, V₂O₅, MoO₃, ormixtures thereof. Process step (b) refers to contacting the feedstockwith hydrogen gas, in the presence of a catalyst at a temperature andfor a time sufficient to form a product mixture comprising anα,ω-C_(n)-diol, wherein n is 5 or greater, and wherein the catalyst isas disclosed herein. In some embodiments, the additive comprises TiO₂.In some embodiments, the additive comprises SiO₂. In some embodiments,the additive comprises ZrO₂. In some embodiments, the additive comprisesAl₂O₃. In some embodiments, the additive comprises MoO₃. In someembodiments, the additive comprises carbon.

In some embodiments, the process for preparing an α,ω-C_(n)-diolcomprises the steps:

(a) providing a feedstock comprising a C_(n) oxygenate;

(b) contacting the feedstock with hydrogen gas, in the presence of acatalyst, and optionally an additive, at a temperature and for a timesufficient to form a product mixture comprising an α,ω-C_(n)-diol;wherein n is 5 or greater;

and wherein the catalyst comprises a metal M1 and a metal M2 or an oxideof M2, and optionally a support, wherein:

M1 is Pd, Pt, or Ir; and M2 is Mo, W, V, Mn, Re, Zr, Ni, Cu, Zn, Cr, Ge,Sn, Ti, Au, or Co; or

M1 is Rh and M2 is Mo, W, V, Mn, Ni, Cu, Zn, Cr, Ge, Sn, Ti, Au, or Zr;or

M1 is Ag, Au or Co; and M2 is Re, Mo, or W; or

M1 is Cu, Pd, Fe, or Ni; and M2 is Re, Mo, Cu, Zn, Cr, Ge, Sn, or W; or

M1 is Ag, Pt, Cu, or Au, and M2 is Ni, Fe, Sn, Ge, or Ir; or

M1 is Co and M2 is Fe; or

M1 is Ni and M2 is Co or Fe; or

M1 is Mn and M2 is Cr; and

wherein the additive comprises WO₃, SiO₂, Al₂O₃, carbon, TiO₂, ZrO₂,SiO₂—Al₂O₃, montmorillonite, SiO₂—TiO₂, tungstated ZrO₂, zeolites, V₂O₅,MoO₃, or mixtures thereof.

The prepared catalyst can be in any physical form typical forheterogeneous catalysts, including but not limited to: powdered (alsoknown as “fluidized”) forms with 0.01-150 μm particle size, formedtablets, extrudates, spheres, engineered particles having uniform 0.5-10mm size, monolithic structures on which surfaces the catalyst isapplied, or combinations of two or more of the above. When a solidsupport is utilized a catalyst containing both M1 and M2, it isdesirable that M1 be intimately associated with the M2 component, asmeasured by transmission electron microscopy with energy dispersivespectroscopy. It is further preferable that the particle size of the M1component be less than 10 nm and most preferably less than 3 nm asmeasured by the same techniques. In this case, particle size of the M1component may be interpreted as particle size of a mixture of the M1 andM2 components, an alloy of the M1 and M2 components, a particle of theM1 component adjacent to a particle of the M2 component, or a particleof the M1 component on the support which contains the M2 component.

The catalyst may be present in any weight ratio to the feedstocksufficient to catalyze the hydrodeoxygenation, generally in the range of0.0001:1 to 1:1, preferably 0.001:1 to 0.5:1 for batch reactions. Forcontinuous reactions, the same ratios are appropriate where the weightratio of feed to catalyst is defined as weight of C_(n) oxygenate feedprocessed per weight of catalyst.

Useful temperatures for the processes are between about 30° C. and about300° C. In some embodiments, the temperature is between and optionallyincludes any two of the following values: 30° C., 40° C., 50° C., 60°C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C.,150° C., 160° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C.,230° C., 240° C., 250° C., 260° C., 270° C., 280° C., 290° C., and 300°C. It is expected that with some catalysts, temperatures above about300° C. could be used.

The process is conducted by contacting a Cn oxygenate feed with hydrogenin the presence of the catalyst for a time sufficient to form a productmixture comprising an α,ω-C_(n)-diol. The mole ratio of hydrogen to feedis not critical as long as sufficient hydrogen is present to produce thedesired α,ω-C_(n)-diol. Hydrogen is preferably used in excess, and mayoptionally be used in combination with an inert gas such as nitrogen orargon. If an inert gas is used in combination with the hydrogen, theamount of the inert gas should be such that it does not negativelyimpact the formation of the product mixture. The pressure of the processmay be between about 300 kPa and about 25,000 kPa, for example between5000 and 150,000 kPa. In some embodiments, the pressure of the processis between and optionally includes any two of the following values: 300;500; 1000; 1500; 2000; 2500; 3000; 3500; 4000; 4500; 5000; 10,000;15,000; 20,000; and 25,000 kPa.

The process is typically conducted in the presence of a solvent, whichmay serve to reduce the viscosity of the system to improve fluidity ofthe catalyst in the reaction vessel and/or to remove the heat ofreaction and improve the performance of the process. Polar solvents arepreferred. The solvent may be present in a range of 1% to 95% by weightof the total reaction mixture, excluding the catalyst.

The reaction products may be isolated or purified by any common methodsknown in the art including but not limited to distillation, wiped filmevaporation, chromatography, adsorption, crystallization, and membraneseparation.

It will be appreciated that the processes disclosed herein can also beutilized to prepare useful intermediates or byproducts in the synthesisof the α,ω-diols through optimization of the process parameters.Examples of intermediates that can be prepared during synthesis of1,5-pentanediol and/or 1,6-hexanediol include but are not limited tofuran dimethanol: tetrahydrofuran dimethanol;tetrahydropyran-2-methanol; levoglucosanol; and furfuryl alcohol.Examples of byproducts which can be obtained during synthesis of1,5-pentanediol and/or 1,6-hexanediol include but are not limited toisomeric hexanols; isomeric pentanols; 1,5-hexanediol; 1,2-hexanediol;2-methyltetrahydropyran; 2,5-dimethyltetrahydrofuran;1,2-cyclohexanediol; 1,2-cyclopentanediol; cyclohexanol, and mixturesthereof.

The α,ω-C_(n)-diols obtained by the processes disclosed herein can beconverted to industrially useful materials such asα,ω-C_(n)-diaminoalkanes. For example, 1,5-pentanediol and1,6-hexanediol can be reductively aminated to 1,5-pentanediamine(1,5-diaminopentane) and 1,6-hexanediamine (1,6-diaminohexane),respectively, by methods known in the art. See, for example, U.S. Pat.No. 3,215,742; U.S. Pat. No. 3,268,588; and U.S. Pat. No. 3,270,059.

In some embodiments, the processes disclosed herein further comprise thesteps:

(c) optionally, isolating the α,ω-C_(n)-diol from the product mixture;

(d) contacting the α,ω-C_(n)-diol with ammonia and hydrogen in thepresence of a reductive amination catalyst at a temperature and for atime sufficient to form a second product mixture comprising an α,ω-C_(n)diaminoalkane; and

(e) optionally, isolating the α,ω-C_(n)-diaminoalkane from the secondproduct mixture.

In one embodiment, the α,ω-C_(n)-diaminoalkane comprises1,6-diaminohexane. In one embodiment, the α,ω-C_(n)-diaminoalkanecomprises 1,5-diaminopentane.

The reductive amination catalyst contains at least one element selectedfrom Groups IB, VIB, VIIB, and VIII of the Periodic Table, for exampleiron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, copper,chromium, iridium, or platinum. The elements may be in the zerooxidation state or in the form of a chemical compound. The reductiveamination catalyst may be supported, unsupported or Raney-type. In oneembodiment, the reductive amination catalyst contains ruthenium. In oneembodiment, the reductive amination catalyst contains nickel. In oneembodiment, the reductive amination catalyst is Raney nickel. In oneembodiment, the reductive amination catalyst is Raney copper. In oneembodiment, the reductive amination catalyst is Raney cobalt.

The reductive amination step is conducted by contacting theα,ω-C_(n)-diol, or a product mixture comprising the α,ω-C_(n)-diol, withammonia and hydrogen in the presence of the catalyst for a timesufficient to form a second product mixture comprising anα,ω-C_(n)-diaminoalkane. Useful temperatures for the reductive aminationstep are in the range of about 40° C. to 300° C., for example in therange of about 75° C. to 150° C. Typically pressures are in the range ofabout 2 MPa to 35 MPa, for example in the range of about 4 MPa to 12MPa. The molar ratio of hydrogen to the α,ω-C_(n)-diol is typicallyequal to or greater than 1:1, for example in the range of 1:1 to 100:1,or in the range of 1:1 to 50:1.

The reductive amination step is typically performed in liquid ammoniasolvent. The ammonia is used in stoichiometric excess with reference tothe α,ω-C_(n)-diol. Typically, a molar ratio of 1:1 to 80:1 of ammoniato the α,ω-C_(n)-diol can be used, for example a molar ratio in therange of 10:1 to 50:1. Optionally, an additional solvent such as water,methanol, ethanol, butanol, pentanol, hexanol, an, ester, a hydrocarbon,tetrahydrofuran, or dioxane, can be used. The weight ratio of theadditional solvent to the α,ω-C_(n)-diol is typically in the range of0.1:1 to 5:1.

The reductive amination step can be performed in a fixed bed reactor orin a slurry reactor, for example a batch, continuous stirred tankreactor or bubble column reactor. The α,ω-C_(n)-diamine may be isolatedfrom the second product mixture by any common methods known in the art,for example fractional distillation under moderate vacuum.

EXAMPLES

The processes described herein are illustrated in the followingexamples. From the above discussion and these examples, one skilled inthe art can ascertain the essential characteristics of this invention,and without departing from the spirit and scope thereof, can makevarious changes and modifications to adapt it to various uses andconditions.

The following abbreviations are used in the examples: “° C.” meansdegrees Celsius; “wt %” means weight percent; “g” means gram(s); “min”means minute(s); “h” means hour(s); “μL” means microliter(s); “wt %”means weight percent; “RV(s)” means reaction vessel(s); “psi” meanspounds per square inch; “mg/g” means milligram(s) per gram; “μm” meansmicrometer(s); “mL” means milliliter(s); “mm” means millimeter(s); “cm”means centimeter(s); “mL/min” means milliliter(s) per minute; “kPa”means kilopascal; “MPa” means megapascal(s); “m²/g” means square metersper gram; “GC” means gas chromatography; “MS” means “mass spectrometry”;“Cony” means conversion; “sel” means selectivity; “LHSV” means liquidhourly space velocity; “GTO” means gas to oil ratio; “12HD” means1,2-hexanediol; “12CHD” means 1,2-cyclohexanediol; “c12CHD” meanscis-1,2-cyclohexanediol; “1H” means 1-hexanol; “1P” means 1-pentanol;“15HD” means 1,5-hexanediol.

Materials

All commercial materials were used as received unless stated otherwise.1,2,6-hexanetriol (>=97 GC area % purity) was obtained from EvonikDEGUSSA GmBH, Marl, Germany. Tetrahydrofuran-2,5-dimethanol (97% purity)was obtained from Aldrich. 2-Hydroxymethyltetrahydropyran (98% purity)was obtained from Aldrich. N-Hexanol (98% purity) was obtained fromAldrich. Deionized water (DI) (pH=5.2) was used unless otherwiseindicated. Commercially available metal salts used in catalystpreparation are listed in Table 1. Catalyst supports and zeolites usedfor catalyst preparation are described in Tables 2 and 3.

TABLE 1 Commercially Available Metal Salts Used in Catalyst PreparationMetal Salt Source Rhodium (III) Chloride Hydrate StremTetraammineplatinum (II) Nitrate Aldrich Ruthenium (III) ChlorideHydrate Alfa Aesar Copper (II) Nitrate Hydrate Alfa Aesar PalladiumNitrate Alfa Aesar Nickel (II) nitrate Hexahydrate Aldrich Iridium (IV)Chloride Hydrate Aldrich Tin (II) Chloride Dihydrate Aldrich HydrogenTetrachloroaurate (III) Trihydrate Aldrich Silver Nitrate Aldrich Iron(III) Nitrate Nonahydrate Aldrich Cobalt (II) Nitrate HexahydrateAldrich Ammonium Perhenate Aldrich Ammonium Tungsten Oxide Hydrate AlfaAesar Ammonium Molybdate Hydrate Alfa Aesar Manganese (II) NitrateHydrate Alfa Aesar Ammonium Vanadium Oxide Alfa Aesar ZirconiumDinitrate Oxide Hydrate Alfa Aesar Chromium (III) Nitrate NonahydrateAldrich

TABLE 2 Supports Used in Catalyst Syntheses and Their Commercial SourcesMaterial Vendor Identifier SiO₂ EMD Silica Gel 60 Al₂O₃ J. T. BakerCelite ® 545 EMD Celite ®545 TiO₂ Evonik Industries Aerolyst-7708 TiO₂Evonik Industries Aerolyst-7711 MgO Spectrum Cerium(IV)Oxide Alfa AesarNiobium (II) Oxide Alfa Aesar WO₃ Aldrich ZrO₂ Saint-Gobain NorProSZ31107

For catalysts comprising a TiO₂ support, the TiO₂ was Aerolyst-7708 fromEvonik Industries unless otherwise indicated.

TABLE 3 Commercially Available Zeolites Used in Catalyst Syntheses andTheir Commercial Sources Material Descrip- Identifier tion VendorComposition/Characteristics Silica-Alumina Aldrich Zeolyst CP814EZeolite- Zeolyst SiO₂/Al₂O₃ Mole Ratio: 25 Beta Nominal Cation Form:Ammonium Na₂O Weight %: 0.05 Surface Area, m²/g: 680 Zeolyst CBV ZSM-5Zeolyst SiO₂/Al₂O₃ Mole Ratio: 30 3024E type Nominal Cation Form:Ammonium Na2O Weight %: 0.05 Surface Area, m²/g: 400 Zeolyst ZeoliteZeolyst SiO₂/Al₂O₃ Mole Ratio: 360 CP811C-300-H- Beta Nominal CationForm: Beta MR 350 Hydrogen Na2O Weight %: 0.05 Surface Area, m²/g: 620H—Y 120/20 Zeolite Degussa SiO₂/Al₂O₃ = 129 H—Y Zeocat ZSM-5 ZSM-5Chemie PZ-2/50H Uetikon LSX LSX Zeochem Purmol LSX Zeolite PowderMolecular Sieve; mNaO•mAl₂O₃•ySiO₂•xH₂O NH₄ Mordenite Mordenite CBV-20ACBV 30011G ZSM-5 Zeolyst ZSM-5 PZ-2/50 H ZSM-5 Chemie ZSM-5 Uetikon CBV720 Zeolite Y Zeolyst SiO₂/Al₂O₃ Mole Ratio: 30 Nominal Cation Form:Hydrogen Na2O Weight %: 0.03 Unit Cell Size, A: 24.28 Surface Area,m²/g: 780 CBV 2802 H-ZSM-5 Zeolyst PZ-2/50 H H-ZSM-5 Chemie Uetikon CBV780 Zeolite Y Zeolyst SiO₂/Al₂O₃ Mole Ratio: 80 Nominal Cation Form:Hydrogen Na2O Weight %: 0.03 Unit Cell Size, A: 24.24 Surface Area,m²/g: 780 PZ-2/300 H H-ZSM-5 Chemie Uetikon PZ-2/250 H H-ZSM-5 ChemieUetikon CBV 901 Zeolite Y Zeolyst SiO₂/Al₂O₃ Mole Ratio: 80 NominalCation Form: Hydrogen Na2O Weight %: 0.03 Unit Cell Size, A: 24.24Surface Area, m²/g: 700 CBV 90A H- Zeolyst mordenite CBV 20A NH4- PQMordenite

The mixed support TiO₂-CBV780 was prepared as follows: 0.46 g ofAerolyst 7708 TiO₂ (Evonik) and 0.46 g of Zeolyst CBV780 (Zeolyst Int)that had been ground and passed through a 0.0165″ mesh sieve werethoroughly mixed together with a mortar and pestle.

Analytical Methods

Reactor feed solutions and reaction product solutions were analyzed bygas chromatography using standard GC and GC/MS equipment: Agilent 5975C,HP5890, Stabilwax Column Restek Company Bellefonte, Pa. (30 m×0.25 mm,0.5 micron film thickness). Chemical components of reaction productmixtures were identified by matching their retention times and massspectra to those of authentic samples.

Product mixture distribution, percent conversion, percent selectivity,and % yield are defined as follows:

${{Product}\mspace{14mu} {Mixture}\mspace{14mu} {Distribution}} = \frac{{Area}\mspace{14mu} \% \mspace{14mu} {of}\mspace{14mu} {Compound}}{{Sum}\mspace{14mu} {of}\mspace{14mu} {Area}\mspace{14mu} \% \mspace{14mu} {of}\mspace{14mu} {all}\mspace{14mu} {observed}\mspace{14mu} {compounds}}$

where area percents were determined from gas chromatographic analysis.

${\% \mspace{14mu} {Conversion}} = \frac{\begin{matrix}{100*( {{{mol}\mspace{14mu} {starting}\mspace{14mu} {material}\mspace{14mu} {charged}} -} } \\ {{mol}\mspace{14mu} {starting}\mspace{14mu} {material}\mspace{14mu} {remaining}} )\end{matrix}}{{mol}\mspace{14mu} {starting}\mspace{14mu} {material}\mspace{14mu} {charged}}$${\% \mspace{14mu} {Selectivity}} = \frac{100*{mol}\mspace{14mu} {of}\mspace{14mu} {product}\mspace{14mu} {compound}}{\begin{matrix}( {{{mol}\mspace{14mu} {starting}\mspace{14mu} {material}\mspace{14mu} {charged}} -}  \\ {{mol}\mspace{14mu} {starting}\mspace{14mu} {material}\mspace{14mu} {remaining}} )\end{matrix}}$${\% \mspace{14mu} {Yield}} = \frac{100*{mol}\mspace{14mu} {product}\mspace{14mu} {compound}}{{Mol}\mspace{14mu} {starting}\mspace{14mu} {material}\mspace{14mu} {charged}}$

where mol of compounds were determined from calibrated GC methods.

In referring to M1/WO₃ catalysts, M1% means the weight percent of M1based on the prepared catalyst weight. For example, 4% Pt/WO₃ means 0.04g of Pt and 0.96 g of WO₃ in 1 g of catalyst.

In referring to M1/WO_(x) catalysts, M1:W means the molar ratio of M1 toW based on the weight of prepared catalyst M1/WO_(x). For example, 1:05Pt/WO_(x) means in any given weight of the catalyst the atomic molarratio of Pt to W is 1:0.5.

In referring to M1M2/support catalysts, M1% means the weight percent ofM1 based on the prepared catalyst weight, and M1/M2 is the molar ratioof M1 to M2 unless otherwise noted. For example, 4% PtW/TiO₂ (Pt/W=1)means one gram of catalyst contains 0.04 g of Pt and has a Pt/W molarratio of 1.

In referring to PtW/TiO₂ (x % Pt y % W) catalysts, x % and y % representthe weight percentages of Pt and W, respectively. For example PtW/TiO₂(1% Pt, 4% W) means one gram of catalyst contains 0.01 g of Pt and 0.04g of W.

For all the catalyst syntheses, only one metal salt was used as theprecursor for each metal in the catalyst; the metal salts are given inTable 1.

Preparation of M1/WO₂ Catalysts

A Pt/WO₃ catalyst containing 4 wt % Pt was synthesized as follows. 0.48Grams of WO₃ support that had been ground with a mortar and pestle andpassed through a 420 micron mesh sieve was placed into a glass vial.Tetraammineplatinum (II) nitrate (0.039 g) dissolved in 0.5 mL of waterwas then added to the WO₃ to impregnate Pt onto the solid support viaincipient wetness. The mixture was stirred for 15 minutes, then driedovernight under vacuum at 110° C. After cooling to room temperature, thesolid was calcined in air at 400° C. for 4 hours.

Other M1/WO₃ catalysts were prepared according to the above procedureusing the appropriate amounts of corresponding M1-containing metal saltslisted in Table 1. M1/WO₃ catalysts were used in Examples 1-11.

Examples 1-11 Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-HexanediolUsing M1/WO₃ Catalysts in Batch Mode (without Pre-Reduction of theCatalyst)

In each of Examples 1-11, the conversion of 1,2,6-hexanetriol (126HT) toa reaction mixture comprising 1,6-hexanediol (16HD) was performedaccording to the following procedure. Approximately 1 g of an aqueoussolution of 126HT (5 weight percent) and approximately 50 mg of theM1/WO₃ catalyst indicated in Table 1 were placed into a 1.5 mL pressurevessel containing a stir bar. The vessel was charged with H₂ to 1000psig H₂ and heated to the reaction temperature shown in Table 4. Thereaction pressure and temperature were maintained for 4 hours. Thevessel was then cooled to room temperature. The reaction mixture wasfiltered and the reaction solution analyzed using GC methods calibratedwith internal standards. Results are presented in Table 4.

TABLE 4 Conversion of 126HT to 16HD Using M1/WO₃ Catalysts at 1000 psigH₂ % Yield Temp Catalyst % of Example (° C.) M1/WO₃ M1 wt % Conversion16HD 1 180 Pt/WO₃ 2 65.3 46.4 2 180 Pd/WO₃ 0.5 7.5 2.1 3 250 Fe/WO₃ 429.7 6.4 4 250 Ni/WO₃ 4 23.4 2.4 5 250 Cu/WO₃ 10 100.0 37.4 6 250 Ni/WO₃10 100.0 5.0 7 160 Rh/WO₃ 2 116 50.4 8 160 Ir/WO₃ 4 115 14.3 9 250Ru/WO₃ 1 99 56.3 10 250 Ag/WO₃ 1 96 39.9 11 250 Au/WO₃ 4 98 43.9

Preparation of M1WO_(x) Catalysts

A PtWO_(x) (Pt:W=0.04:1) catalyst was synthesized as follows. Ammoniumtungsten oxide hydrate, (NH₄)₁₀W₁₂O₄₁.5H₂O, (0.680 g) was dissolved in40.0 mL of water. To this was added a solution of tetraammineplatinum(II) nitrate (0.0396 g dissolved in 0.5 mL of water). A white solidprecipitated immediately upon the addition. The slurry was mixed on arotary evaporator for 30 minutes, and then placed into a vacuum oven anddried at 110° C. overnight. After cooling to room temperature, thematerial was transferred to a ceramic boat and calcined in air at 400°C. for three hours.

Other M1WO_(x) catalysts were prepared according to the above procedureusing the appropriate amounts of M1-containing metal salt and(NH₄)₆H₂W₁₂O₄₁.5H₂O to attain the desired M1:W molar ratios. M1/WO_(x)catalysts were used in Examples 12-16.

Examples 12-16 Hydrodeoxygenation of 126HT to 16HD Using M1/WO_(x)Catalysts

Examples 12-16 were performed following the procedure of Examples 1-11except using the M1/WO_(x) catalysts and temperatures indicated in Table5. Results are presented in Table 5.

TABLE 5 Conversion of 126HT to 16HD Using M1/WO_(x) Catalysts at 1000psig H₂ % Yield Temp Catalyst M1:W % of Example (° C.) M1/WO_(x) molarratio Conversion 16HD 12 140 Pt/WO_(x) Pt:W = 1:1 85.0 71.5 13 250Fe/WO_(x) Fe:W = 0.5:1 100.0 7.5 14 250 Pd/WO_(x) Pd:W = 0.5:1 100.0 9.415 250 Cu/WO_(x) Cu:W = 0.5:1 100.0 20.5 16 250 Ni/WO_(x) Ni:W = 1:1100.0 1.5

Preparation of M1M2/Support Catalysts Catalyst Preparation Method A

A PtW/TiO₂ catalyst containing 4 wt % Pt and having a molar ratio ofPt:W of 1:1 was prepared according to the following procedure.

An aqueous solution of tetraammineplatinum (II) nitrate (0.079 gdissolved in 1.0 mL of water) was added to 0.92 g of TiO₂ (Aerolyst7708) that had been ground with a mortar and pestle, passed through a400 micron mesh sieve, and then wetted with water (1.0 mL). Theresulting slurry was stirred at room temperature for 15 minutes, thendried overnight in a vacuum oven at 110° C. The solid material wasallowed to cool to room temperature, and then wetted with 1.0 mL ofwater. To this was added 0.0535 g of ammonium tungsten oxide hydratedissolved in 3.0 mL of water. The mixture was stirred for 15 minutes atroom temperature, then dried overnight in a vacuum oven at 110° C. Aftercooling to room temperature, the material was transferred to a ceramicboat and calcined in air at 400° C. for three hours.

Other M1M2/support catalysts were prepared following the above procedurebut using appropriate amounts of M1- and M2-containing metal salts fromTable 1 and a selected support from Table 2 or Table 3. The catalystsprepared according to this method were used in batch modehydrodeoxygenation Examples described below.

Examples 17-54 Hydrodeoxygenation of 126HT to 16HD Using M1M2/SupportCatalysts

Examples 17-54 were performed following the procedure of Examples 1-11except using the M1M2/support catalysts, temperatures, and reactionpressures indicated in Table 6. Results are presented in Table 6.

TABLE 6 Conversion of 126HT to 16HD Using M1M2/Support CatalystsCatalyst M1 M1/M2 % Temp P (M1M2/ wt molar % Yield Ex (° C.) (psig)support)* % ratio Conv 16HD 17 250 1500 CuW/TiO₂ 4 2 100.0 35.9 18 2501500 CuNi/TiO₂ 3 1 99.2 26.9 19 250 1000 CuZn/TiO₂ 10 2 6.1 2.7 20 2501000 CuCr/TiO₂ 4 1 35.4 2.4 21 250 1000 FeCr/CBV780 4 12 32.3 1.3 22 2501000 FeCr/TiO₂ 4 1 18.7 0.6 23 250 1000 FeZn/TiO₂ 10 2 4.0 0.6 24 2501000 NiW/TiO₂ 4 1 71.4 35.8 25 250 1000 NiCr/CBV780 4 12 84.0 7.3 26 2501000 NiZn/TiO₂ 10 2 47.7 4.6 27 250 1000 NiCr/TiO₂ 4 12 100.0 4.2 28 2501000 PdReTiO₂ 4 1 93.3 41.5 29 260 1000 PdW/TiO₂ 4 1 41.6 23.3 30 2501500 PdMo/TiO₂ 4 1 41.7 19.8 31 250 1000 PdCr/CBV780 4 12 1.3 19.3 32250 1500 PdMo/H—Y 4 1 6.0 18.8 33 180 1040 PdMo/H—Y 4 1 37.2 9.5 34 2501000 PdCr/TiO₂ 4 12 100.0 3.7 35 250 1000 PdZn/TiO₂ 10 2 100.0 0.9 36250 1000 RuCu/CBV780 4 1 100.0 14.0 37 200 1000 RuCu/TiO₂ 4 1 37.4 17.838 200 1000 RuPd/CBV780 4 1 100.0 0.3 39 200 1000 RuFe/CBV780 4 1 11.40.4 40 200 1000 RuCu/CBV780 4 1 100.0 10.3 41 250 1500 PtMn/H—Y 4 1100.0 36.8 42 250 1100 PtCo/CBV780 4 2 100.0 17.0 43 180 1000PtZr/CBV780 4 2 100.0 14.0 44 140 1000 PtCr/TiO₂ 4 1 4.9 1.3 45 250 1500PtCo/TiO₂ 4 1 100.0 1.3 46 250 1500 PtCo/H—Y 4 1 65.7 1.1 47 140 1000PtCr/CBV780 4 1 13.3 0.5 48 140 1000 PtCr/SiO₂ 4 1 8.6 0.1 49 250 1500AgW/TiO₂ 4 1 9.4 29.1 50 200 1000 AgRe/TiO₂ 4 1 12.2 25.9 51 250 1600AgRe/SiO₂ 4 1 50.9 23.6 52 250 1600 AgRe/H—Y 4 1 100.0 22.6 53 250 1600AgRe/Al₂O₃ 4 1 42.2 18.0 54 180 1000 AgMo/TiO₂ 4 1 99.4 3.2 *For thecatalysts comprising a TiO₂ support, the TiO₂ was Aerolyst-7708 fromEvonik Industries.

Examples 56-64 Hydrodeoxygenation of THPM to 16HD Using M1M2/SupportCatalysts

Examples 56-64 were performed following the procedure of Examples 1-11except using an aqueous solution of 5 wt %2-hydroxymethyltetrahydropyran (THPM) as the substrate, the M1M2/supportcatalysts, and temperatures indicated in Table 7. Results are presentedin Table 7.

TABLE 7 Conversion of THPM to 16HD Using M1M2/Support Catalysts at 1000psig H₂. Catalyst * M1 M1/M2 % Yield Temp (M1M2/ wt molar % of Ex (° C.)Support) M1 % ratio Conversion 16HD 56 250 AgNi/CBV780 Ag 4 1 50.0 16.257 250 AgNi/Al₂O₃ Ag 4 1 22.2 10.4 58 250 AuNi/CBV780 Au 4 1 17.3 7.4 59250 CuNi/CBV780 Cu 4 1 25.3 7.3 60 250 CuNi/TiO₂ Cu 4 1 19.4 4.7 61 250CuW/Al₂O₃ Cu 4 1 9.0 4.7 62 250 CuNi/TiO₂ Cu 4 1 20.3 2.9 63 250PtFe/SiO₂ Pt 4 1 22.8 1.6 64 250 PtFe/Al₂O₃ Pt 4 1 5.1 1.2 * Forcatalysts containing TiO₂, the TiO₂ supports were Aerolyst-7708 exceptwhere indicated otherwise.

Examples 65-70 Hydrodeoxygenation of 126HT to 16HD Using M1M2/SupportCatalysts

Examples 65-77 were performed following the procedure of Examples 1-11except using 2.5 wt % 126HT as the substrate, the temperatures, and theM1M2/support catalysts indicated in Table 8. Results are presented inTable 8.

TABLE 8 Conversion of 126HT to 16HD Using M1M2/Support CatalystsCatalyst * M1 M1/M2 % Sel Temp (M1M2/ wt molar % to Ex (° C.) Support)M1 M2 % ratio Conv 16HD 65 220 AgNi/TiO₂ Ag Ni 4 1 83 53 66 220PtFe/TiO₂ Pt Fe 4 1 53 39 67 250 CuFe/TiO₂ Cu Fe 4 1 37 56 68 250AuNi/TiO₂ Au Ni 4 1 50 51 69 250 AuIr/TiO₂ Au Ir 4 1 33 25 70 250IrW/TiO₂ Ir W 4 1 76 32 * For these Examples, the TiO₂ supports wereAerolyst-7711 except for the catalyst of Example 70, which containedAerolyst-7708 TiO₂.

Preparation of PtW/TiO₂ Catalysts Containing (x % Pt, % W) CatalystPreparation Method B

A PtW/TiO₂ catalyst containing 4 wt % Pt and 4 wt % W was prepared asfollows. Ammonium tungsten oxide hydrate (0.170 g) dissolved in 9.5 mLof water was added to 2.88 g of TiO₂ (Aerolyst-7708 from EvonikIndustries) that had been previously wetted with 2.8 mL of water. Themixture was stirred for 15 minutes and then excess water was removedunder reduced pressure using a rotary evaporator and an 80° C. waterbath. The resulting solid was then dried in a vacuum oven overnight at110° C. The solid was then calcined in air at 400° C. for three hours.

0.46 Grams of the calcined solid was wetted with 0.5 mL of water, andthen impregnated with 0.0396 g of tetraammineplatinum (II) nitrate in0.5 mL of water. The mixture was stirred for 15 minutes, then driedovernight under vacuum at 110° C. After cooling to room temperature, thematerial was transferred to a ceramic boat and calcined in air at 400°C. for three hours.

Other PtW/TiO₂ catalysts containing 1, 2, or 4 wt % Pt in combinationwith 4, 10, 15, or 20 wt % W were prepared according to CatalystPreparation Method B using the appropriate amounts of ammonium tungstenoxide hydrate, TiO₂, and tetraammineplatinum (II) nitrate. Catalystsprepared by Method B were used in Examples 78-89. Results are given inTable 9.

Examples 71-82 Hydrodeoxygenation of 126HT to 16HD Using PtW/TiO₂Catalysts Containing (x % Pt, y % W)

Examples 71-82 were performed following the procedure of Examples 1-11except using the PtW/TiO₂ catalysts containing (x % Pt, y % W) andtemperatures as indicated in Table 9. Results are presented in Table 9.

TABLE 9 Conversion of 126HT to 16HD Using PtW/TiO₂ (x % Pt y % W) at200° C. and 1000 psig H₂. Catalyst * % % Yield Ex wt % M1, wt % M2 Conv16HD THPM 12HD 15HD 1H 1P 71 PtW/TiO₂ 1% Pt, 4% W 93.7 58.3 0.9 1.5 3.715.0 0.6 72 PtW/TiO₂ 2% Pt, 4% W 91.2 58.5 1.0 1.7 4.1 10.4 0.4 73PtW/TiO₂ 4% Pt, 4% W 95.9 50.7 0.2 0.0 2.3 20.6 1.0 74 PtW/TiO₂ 1% Pt,10% W 45.4 22.3 4.9 1.7 1.5 4.1 0.0 75 PtW/TiO₂ 2% Pt, 10% W 71.0 38.43.6 3.1 2.8 7.3 0.0 76 PtW/TiO₂ 4% Pt, 10% W 97.2 49.7 1.1 1.2 3.2 21.90.5 77 PtW/TiO₂ 1% Pt, 15% W 45.6 23.5 4.9 1.7 1.7 4.1 0.0 78 PtW/TiO₂2% Pt, 15% W 72.1 39.0 4.0 1.7 2.7 8.2 0.0 79 PtW/TiO₂ 4% Pt, 15% W 99.341.9 0.7 0.0 1.8 27.7 0.7 80 PtW/TiO₂ 1% Pt, 20% W 53.3 27.9 5.5 2.3 1.95.1 0.0 81 PtW/TiO₂ 2% Pt, 20% W 74.2 40.6 3.6 1.6 3.3 9.0 0.2 82PtW/TiO₂ 4% Pt, 20% W 99.4 40.5 0.5 0.0 2.7 27.1 0.8 * For catalystscontaining TiO₂, the TiO₂ supports were Aerolyst-7708 except whereindicated otherwise.

Examples 83-190 Hydrodeoxygenation of 1,2,6-Hexanetriol to1,6-Hexanediol Using M1M2/Support Catalysts in Batch Mode (withPre-Reduction of the Catalyst)

In each of Examples 83-205, the conversion of 1,2,6-hexanetriol (126HT)to a reaction mixture comprising 1,6-hexanediol (16HD) was performedaccording to the following procedure. Approximately 1 g of an aqueoussolution of 126HT (5 weight percent) and approximately 50 mg of theM1M2/support catalyst indicated in Table 10 were placed into a 1.5 mLpressure vessel containing a stir bar. The vessel was charged with H₂ toa pre-reduction pressure of about 145-150 psi, and then the pressurevessel was heated to the reaction temperature shown in Table 10. Thecontents were stirred for 1 hour before the pressure was raised to 1000psig H₂. The reaction pressure and temperature were maintained for 4hours. The vessel was then cooled to room temperature. The reactionmixture was filtered and the reaction solution analyzed using GC methodscalibrated with internal standards.

Catalysts used in Examples 83-150, temperatures, percent conversion of126HT substrate, and percent selectivity to 16HD are presented in Table10.

Catalysts used in Examples 151-190, temperatures, percent conversion of126HT substrate, percent selectivity to 16HD, and percent selectivity toTHPM are presented in Table 11.

TABLE 10 Conversion of 126HT to 16HD Using M1M2/Support Catalysts M1M2/M1 % Sel Temp wt molar % to Ex ° C. Support * M1 M2 % ratio Conv 16HD83 180 TiO2 Ir Mo 4 1 42.52 22.4 84 160 Al2O3 Ir Re 4 0.5 10.11 23.6 85180 CBV780 Ir Re 4 1 96.66 39.2 86 160 Celite Ir Re 4 0.5 43.51 23.4 87160 H—Y 120/20 Ir Re 4 0.5 80.76 52.4 88 160 MgO Ir Re 4 1 14.89 5.7 89160 SiO2 Ir Re 4 0.5 49.78 18.9 90 180 TiO2 Ir Re 4 1 81.41 39.7 91 160Zeocat ZSM-5 Ir Re 4 0.5 86.22 49.9 PZ-2/50H 92 160 Zeolyst Ir Re 4 0.564.12 20.7 CP814E H-Beta 93 180 CBV780 Ir W 4 1 62.10 26.0 94 160 MgO IrW 4 1 11.03 1.2 95 180 TiO2 Ir W 4 1 54.99 41.3 96 180 TiO2 Pd Mo 4 14.43 14.4 97 160 MgO Pd Re 4 1 1.46 5.5 98 180 TiO2 Pd Re 4 1 23.95 24.399 160 MgO Pd W 4 1 11.52 1.2 100 180 TiO2 Pd W 4 1 13.11 26.2 101 180Silica-Alumina Pt Co 4 0.5 7.17 7.2 102 180 CBV780 Pt Co 4 0.5 29.7019.6 103 180 Al2O3 Pt Mn 4 0.5 3.78 2.8 104 180 Celite Pt Mn 4 0.5 4.022.0 105 180 Silica-Alumina Pt Mn 4 0.5 10.78 11.3 106 180 SiO2 Pt Mn 40.5 4.50 1.6 107 180 CBV780 Pt Mn 4 0.5 82.91 14.9 108 180 Al2O3 Pt Mo 40.5 4.13 13.8 109 180 Celite Pt Mo 4 0.5 4.78 1.6 110 180 Silica-AluminaPt Mo 4 0.5 17.25 27.5 111 180 SiO2 Pt Mo 4 0.5 8.84 17.3 112 180 TiO2Pt Mo 4 0.5 47.45 20.4 113 180 TiO2 Pt Mo 4 1 38.28 24.8 114 180 CBV780Pt Mo 4 0.5 75.65 31.5 115 180 Al2O3 Pt Re 4 0.5 76.72 39.0 116 180CBV780 Pt Re 4 1 90.70 32.2 117 180 Celite Pt Re 4 0.5 3.47 2.4 118 180H—Y 120/20 Pt Re 4 0.5 99.75 23.9 119 180 LSX Pt Re 4 0.5 5.82 1.9 120180 NH4 Mordenite Pt Re 4 0.5 49.07 32.8 CBV-20A 121 180 SiO2 Pt Re 40.5 11.18 14.6 122 180 TiO2 Pt Re 4 0.5 62.58 42.7 123 180 TiO2 Pt Re0.5 1 7.73 33.3 124 180 TiO2 Pt Re 4 1 20.46 39.0 125 180 Zeocat ZSM-5Pt Re 4 0.5 92.74 37.2 PZ-2/50H 126 180 Zeolyst Pt Re 4 0.5 95.71 34.8CBV780 127 180 Zeolyst Pt Re 4 0.5 98.30 38.1 CP814E H-Beta 128 180Al2O3 Pt V 4 0.5 5.84 8.3 129 180 Celite Pt V 4 0.5 8.54 1.1 130 180Silica-Alumina Pt V 4 0.5 9.89 12.3 131 180 SiO2 Pt V 4 0.5 5.31 10.4132 180 CBV780 Pt V 4 0.5 73.13 13.6 133 180 Al2O3 Pt W 4 0.5 7.90 19.4134 180 Celite Pt W 4 0.5 5.19 26.4 135 180 H—Y 120/20 Pt W 4 0.5 75.7422.9 136 180 MgO Pt W 4 1 4.51 2.7 137 180 Silica-Alumina Pt W 4 0.522.73 58.0 138 180 SiO2 Pt W 4 0.5 23.48 56.8 139 180 SiO2 Pt W 10 197.06 70.8 140 180 TiO2 Pt W 4 0.5 60.52 62.1 141 180 TiO2 Pt W 4 185.79 84.1 142 180 TiO2 Pt W 2 1 44.48 75.0 143 180 TiO2-CBV780 Pt W 4 180.82 66.4 144 180 CBV780 Pt W 4 0.5 64.34 35.5 145 180 CBV780 Pt W 4 187.16 42.8 146 180 Al2O3 Pt Zr 4 0.5 4.99 5.5 147 180 Celite Pt Zr 4 0.54.66 2.9 148 180 Silica-Alumina Pt Zr 4 0.5 10.12 11.4 149 180 SiO2 PtZr 4 0.5 2.74 5.7 150 180 CBV780 Pt Zr 4 0.5 61.24 17.4 * For catalystscontaining TiO₂, the TiO₂ supports were Aerolyst-7708 except whereindicated otherwise.

TABLE 11 Conversion of 126HT to 16HD Using M1M2/Support Catalysts M1M2/M1 % Sel % Sel Temp wt molar % to to Ex (° C.) Support * M1 M2 %ratio Conv 1,6 HD THPM 151 180 TiO2 Ir Mo 4 1 42.52 7.06 22.4 152 160Al2O3 Ir Re 4 0.5 10.11 18.79 23.6 153 180 CBV780 Ir Re 4 1 96.66 10.6539.2 154 160 Celite Ir Re 4 0.5 43.51 4.63 23.4 155 160 H—Y 120/20 Ir Re4 0.5 80.76 13.90 52.4 156 160 MgO Ir Re 4 1 14.89 4.61 5.7 157 160 SiO2Ir Re 4 0.5 49.78 3.77 18.9 158 180 TiO2 Ir Re 4 1 81.41 3.06 39.7 159160 Zeocat ZSM-5 Ir Re 4 0.5 86.22 21.33 49.9 PZ-2/50H 160 160 ZeolystCP814E Ir Re 4 0.5 64.12 68.16 20.7 H-Beta 161 180 CBV780 Ir W 4 1 62.1059.65 26.0 162 160 MgO Ir W 4 1 11.03 6.10 1.2 163 180 Al2O3 Pt Mn 4 0.53.78 2.8 15.90 164 180 Celite Pt Mn 4 0.5 4.02 2.0 26.30 165 180Silica-Alumina Pt Mn 4 0.5 10.78 11.3 31.52 166 180 SiO2 Pt Mn 4 0.54.50 1.6 24.68 167 180 CBV780 Pt Mn 4 0.5 82.91 14.9 43.35 168 180 Al2O3Pt Mo 4 0.5 4.13 13.8 18.00 169 180 Celite Pt Mo 4 0.5 4.78 1.6 22.10170 180 Silica-Alumina Pt Mo 4 0.5 17.25 27.5 17.58 171 180 SiO2 Pt Mo 40.5 8.84 17.3 10.70 172 180 TiO2 Pt Mo 4 0.5 52.16 20.2 4.91 173 180CBV780 Pt Mo 4 0.5 75.65 31.5 46.08 174 180 Al2O3 Pt Re 4 0.5 76.72 39.01.92 175 180 CBV780 Pt Re 4 1 90.70 32.2 25.51 176 180 Celite Pt Re 40.5 3.47 2.4 25.73 177 180 H—Y 120/20 Pt Re 4 0.5 99.75 23.9 67.86 178180 LSX Pt Re 4 0.5 5.14 2.1 22.49 179 180 NH4 Mordenite Pt Re 4 0.549.07 32.8 46.65 CBV-20A 180 180 SiO2 Pt Re 4 0.5 11.18 14.6 11.46 181180 TiO2 Pt Re 4 0.5 60.85 32.6 4.72 182 180 TiO2 Pt Re 4 0.5 52.76 35.47.88 183 180 Zeocat ZSM-5 Pt Re 4 0.5 92.74 37.2 42.48 PZ-2/50H 184 180CBV780 Pt Re 4 0.5 95.71 34.8 32.51 185 180 Zeolyst CP814E Pt Re 4 0.598.30 38.1% 37.35 H-Beta 186 180 Al2O3 Pt V 4 0.5 5.84 8.3 14.31 187 180Celite Pt V 4 0.5 8.54 1.1 26.54 188 180 Silica-Alumina Pt V 4 0.5 9.8912.3 38.06 189 180 SiO2 Pt V 4 0.5 5.31 10. 11.13 190 180 CBV780 Pt V 40.5 73.13 13.6 51.56 * For catalysts containing TiO₂, the TiO₂ supportswere Aerolyst-7708 except where indicated otherwise.

Examples 191-228 Hydrodeoxygenation of THPM to 16HD Using M1M2/SupportCatalysts

Examples 191-228 were performed following the procedure of Examples83-150 except using an aqueous solution of 5 wt % THPM as the substrateand the M1M2/support catalysts and temperatures indicated in Table 12.Percent conversion of THPM substrate and percent selectivity to 16HDresults are presented in Table 12.

TABLE 12 Conversion of THPM to 16HD Using M1M2/Support Catalysts at 180°C. and 1000 psig H₂ Catalyst * M1 M2/M1 % Sel (M1M2/ wt Molar % to ExSupport) M1 M2 % Ratio Conv 16HD 191 PtW/Al2O3 Pt W 4 0.5 5.91 38.6 192PtW/Celite Pt W 4 0.5 1.07 0.0 193 PtW/CeO2 Pt W 4 0.5 0.22 39.8 194PtW/H—Y(120/20) Pt W 4 0.5 8.66 75.0 195 PtW/Sibunit # 1 Pt W 4 0.5 1.588.8 Carbon 196 PtW/Sibunit # 2 Pt W 4 0.5 1.64 26.0 Carbon 197PtW/Silica-Alumina Pt W 4 0.5 11.71 78.0 198 PtW/SiO2 Pt W 4 0.5 23.3674.2 199 PtW/TiO2 Pt W 4 0.5 72.67 84.7 200 PtW/TiO2 Pt W 0.5 1 1.08 4.8201 PtW/TiO2 Pt W 4 1 56.95 88.8 202 PtW/Zeolyst CBV780 Pt W 4 1 35.1585.9 203 PtW/Zeolyst CBV780 Pt W 4 0.5 16.60 67.8 204 PtMo/ZeolystCBV780 Pt Mo 4 0.5 17.09 69.2 205 PtRe/Al2O3 Pt Re 4 0.5 47.55 67.7 206PtRe/CBV780 Pt Re 4 1 33.79 60.7 207 PtRe/Celite Pt Re 4 0.5 2.82 1.0208 PtRe/CeO2 Pt Re 4 0.5 0.05 16.2 209 PtRe/H—Y 120/20 Pt Re 4 0.532.68 70.5 210 PtRe/LSX Pt Re 4 0.5 2.52 1.5 211 PtRe/NH4(Mordenite PtRe 4 0.5 21.23 61.7 CBV-20A) 212 PtRe/SiO2 Pt Re 4 0.5 1.75 33.7 213PtRe/TiO2 Pt Re 4 0.5 41.29 73.4 214 PtRe/TiO2-Aerolyst Pt Re 4 1 45.2879.1 7708 215 PtRe/TiO2-Aerolyst Pt Re 0.5 0.5 5.22 73.4 7708 216PtRe/TiO2-Aerolyst Pt Re 0.5 1 5.73 74.0 7708 217 PtRe/Zeocat(ZSM-5) PtRe 4 0.5 41.20 67.7 (PZ-2/50H) 218 PtRe/Zeolyst CBV780 Pt Re 4 0.5 41.3675.7 219 PtRe/Zeolyst CBV780 Pt Re 4 0.75 48.00 74.3 220 PtRe/ZeolystCBV780 Pt Re 4 1 38.39 72.5 221 PtRe/Zeolyst CBV780 Pt Re 0.5 1 4.1156.8 222 PtRe/Zeolyst(CP814E) Pt Re 4 0.5 44.10 73.2 H-Beta MR350 223PtV/Al2O3 Pt V 4 0.5 4.72 3.8 224 PtV/Celite Pt V 4 0.5 0.51 2.8 225PtV/Celite Pt V 4 0.5 2.43 1.0 226 PtV/Silica-Alumina Pt V 4 0.5 1.6529.4 227 PtV/SiO2 Pt V 4 0.5 2.0 12.4 228 PtV/Zeolyst CBV780 Pt V 4 0.55.07 42.6 * In table 12, for catalysts containing TiO₂, the TiO₂supports were Aerolyst-7711 except where indicated otherwise.

Examples 229-255 Hydrodeoxygenation of Tetrahydrofuran-2,5-Dimethanol to16HD Using M1M2/Support Catalysts

Examples 229-255 were performed following the procedure of Examples83-150 except using an aqueous solution of 5 wt %tetrahydrofuran-2,5-dimethanol as the substrate, the temperatures, andthe M1M2/support catalysts indicated in Table 13. These catalystscontained 4 wt % M1 and had an M1/M2 molar ratio of 1. Table 13 alsoincludes percent conversion of tetrahydrofuran-2,5-dimethanol substrateand percent selectivity to 16HD results.

TABLE 13 Conversion of Tetrahydrofuran-2,5-dimethanol to 16HD usingM1M2/Support Catalysts (1000 psig H2; M1 wt % = 4; M1/M2 = 1) Catalyst *% Sel % Sel Temp (M1M2/ % to to Ex (° C.) Support) M 1 M2 Conv 126HT16HD 229 160 IrRe/Al2O3 Ir Re 5.38 25.47 1.0 230 160 IrRe/Celite Ir Re36.47 53.86 1.7 231 160 IrRe/H—Y Ir Re 100.00 11.45 45.5 120/20 232 160IrRe/SiO2 Ir Re 12.09 70.28 1.3 233 160 IrRe/Zeocat Ir Re 19.74 40.294.7 ZSM-5 PZ-2/50H 234 160 IrRe/Zeolyst Ir Re 10.80 45.28 2.9 CP814EH-Beta 235 180 PtMn/ Pt Mn 2.26 57.19 1.6 Silica-Alumina 236 180PtMn/CBV780 Pt Mn 6.52 36.39 3.3 237 180 PtMo/ Pt Mo 11.53 57.11 4.5Silica-Alumina 238 180 PtMo/TiO2 Pt Mo 40.43 54.12 10.8 239 180PtMo/TiO2-7711 Pt Mo 41.16 53.06 10.8 240 180 PtMo/CBV780 Pt Mo 47.3030.12 20.3 241 180 PtRe/Al2O3 Pt Re 69.31 42.97 21.1 242 180 PtRe/H—Y PtRe 38.42 41.45 15.5 120/20 243 180 PtRe/NH₄ Pt Re 22.75 44.65 7.9Mordenite CBV-20A 244 180 PtRe/TiO2 Pt Re 67.62 41.89 17.9 245 180PtRe/TiO2-7711 Pt Re 56.15 52.67 18.8 246 180 PtRe/Zeocat Pt Re 52.657.66 15.3 ZSM-5 PZ-2/50H 247 180 PtRe/CBV780 Pt Re 63.35 22.43 15.9 248180 PtRe/Zeolyst Pt Re 27.12 30.10 8.8 CP814E H-Beta 249 180 PtV/ Pt V3.29 34.85 1.4 Silica-Alumina 250 180 PtW/H—Y Pt W 19.24 41.29 17.9120/20 251 180 PtW/ Pt W 30.01 72.86 10.8 Silica-Alumina 252 180PtW/SiO2 Pt W 21.93 80.30 5.2 253 180 PtW/TiO2 Pt W 53.08 62.81 23.3 254180 PtW/TiO2-7711 Pt W 23.44 81.62 9.6 255 180 PtW/CBV780 Pt W 31.3755.73 19.0 * For catalysts containing TiO₂, the TiO₂ supports wereAerolyst-7708 except where indicated otherwise.

Example 256 Conversion of 1,2,6-Hexanetriol to a Reaction MixtureComprising 1,6-Hexanediol in a Continuous Trickle Bed Reactor

A M1M2/support catalyst containing Pt/W (1:1) supported on TiO₂ wasprepared according to the following procedure. 32.2 Grams of catalystsupport (Aerolyst 7708 TiO₂) as received from the vendor was firstcrushed and sieved to a particle size range of 1 to 1.2 mm. The supportwas then added to a flask and wetted with approximately 32 mL ofdeionized water. The wetted support was then mixed with an additional 35mL deionized water containing 2.77 g of dissolved tetraammineplatinum(II) nitrate M1-salt to form a slurry. The support/M1-salt slurry wasthen stirred for 15 minutes. The flask was then placed onto a rotaryevaporator and water was removed at 80° C. under reduced pressure untilthe catalyst reached incipient wetness. The catalyst was then furtherdried overnight (17 h) in a vacuum oven held at 110° C. The driedcatalyst was allowed to cool to room temperature, then was wetted againwith of 35 mL of deionized water. The wetted support was then mixed withan additional 105 mL of deionized water containing 1.87 g of dissolvedammonium tungsten oxide hydrate M2-salt to form a slurry. The slurry wasthen stirred for 15 minutes. The flask was then placed onto a rotaryevaporator and water was removed at 80° C. under reduced pressure untilthe catalyst reached incipient wetness. The catalyst was then furtherdried overnight (17 h) in a vacuum oven held at 110° C. After cooling toroom temperature, the material was transferred to a ceramic boat andcalcined in air at 400° C. for three hours. The catalyst was used tohydrodeoxygenate 126HT to a reaction mixture comprising 16HD accordingto the following procedure.

The conversion of 126HT to a reaction mixture comprising 16HD wasconducted in a vertical 21 mm internal diameter 316 stainless steelfixed bed reactor. The reactor was initially loaded with 21.14 g of thePt/W (1:1) on Aerolyst 7708 TiO₂ catalyst, which was held in place byabout 20 g of 1 mm inert corundum spheres on both sides of the catalystbed.

The reactor was pressurized with nitrogen to 1000 psi using a flow rateof 192 sccm. The run was started by introducing a 4.0 wt % 126HT inwater feed to the inlet at the top of the reactor at a flow rate of0.192 mL min-1. At the same time the reactor heating was started. Oncethe reactor reached 140° C. the nitrogen feed was turned off and thehydrogen feed was simultaneously started with a flow rate of 192 sccm.

During the run liquid product was collected in a 1 L chilled productreceiver. After 2 days on stream the reactor temperature was increasedto 160° C. After 5 days on stream a one hour averaged steady statesample was collected by first draining the product receiver and thenallowing it to refill over a one hour time period. The sample was thendrained from the product receiver, weighed and analyzed by gaschromatography. All major compounds were identified and quantified usinganalytical standards. The 11.55 g sample solution contained 0.141 g of126HT (69.7% conversion based on 126HT fed) and 0.205 g of 16HD (50.0%molar yield based on 126HT fed).

Example 257 Conversion of 1,2,6-Hexanetriol,2-Hydroxymethyltetrahydropyran, and Tetrahydrofuran-2,5-DimethanolFeedstocks (Separately) to a Reaction Mixture Comprising 1,6-Hexanediolin a Continuous Trickle Bed Reactor

A M1M2/support catalyst containing Ni/W (1:1) supported on TiO₂ wasprepared according to the following procedure. 28.8 Grams of catalystsupport (Aerolyst 7708 TiO₂) as received from the vendor was firstcrushed and sieved to a particle size range of 1 to 1.2 mm. The supportwas then added to a flask and wetted with approximately 30 mL ofdeionized water. The wetted support was then mixed with an additional 10mL deionized water containing 5.95 g of dissolved nickel (II) nitratehexahydrate M1-salt to form a slurry. The support/M1-salt slurry wasthen stirred for 15 minutes. The flask was then placed onto a rotaryevaporator and water was removed at 80° C. under reduced pressure untilthe catalyst reached incipient wetness. The catalyst was then furtherdried overnight (17 h) in a vacuum oven held at 110° C. The driedcatalyst was allowed to cool to room temperature, then was wetted againwith of 30 mL of deionized water. The wetted support was then mixed withan additional 300 mL of deionized water containing 5.34 g of dissolvedammonium tungsten oxide hydrate M2-salt to form a slurry. The slurry wasthen stirred for 15 minutes. The flask was then placed onto a rotaryevaporator and water was removed at 80° C. under reduced pressure untilthe catalyst reached incipient wetness. The catalyst was then furtherdried overnight (17 h) in a vacuum oven held at 110° C. After cooling toroom temperature, the material was transferred to a ceramic boat andcalcined in air at 400° C. for three hours. The catalyst was used tohydrodeoxygenate several oxygenated feedstocks in sequence to a reactionmixture comprising 16HD according to the following procedure.

A vertical 21 mm internal diameter 316 stainless steel fixed bed reactorwas initially loaded with 20.04 g of the Ni/W (1:1) on Aerolyst 7708TiO₂ catalyst held in place by about 20 g of 1 mm inert corundum sphereson both sides of the catalyst bed.

The reactor was pressurized with nitrogen to 1000 psi using a flow rateof 158 sccm. The run was started by introducing a 4.7 wt % 126HT inwater feed to the inlet at the top of the reactor at a flow rate of0.158 ml min-1. At the same time the reactor heating was started. Oncethe reactor reached 235° C. the nitrogen feed was turned off and thehydrogen feed was simultaneously started with a flow rate of 158 sccm.

During the run liquid product was collected in a 1 L chilled productreceiver. After 9 days on stream the reactor temperature was increasedto 250° C. and the reactor pressure was increased to 1500 psi. After 10days on stream a one hour averaged steady state sample was collected byfirst draining the product receiver and then allowing it to refill overa one hour time period. The sample was then drained from the productreceiver, weighed and analyzed by gas chromatography. All majorcompounds were identified and quantified using analytical standards. The18.54 g sample solution contained 0.069 g of 126HT (92.1% conversionbased on 126HT fed) and 0.229 g of 16HD (29.5% molar yield based on126HT fed).

After 57 days on stream the liquid feed was switched to a 4.7 wt %2-hydroxymethyltetrahydropyran in water solution with a flow rate of0.158 mL min⁻¹. After 58 days on stream a one hour averaged steady statesample was collected. The 14.67 g sample solution contained 0.595 g of2-hydroxymethyltetrahydropyran (14.7% conversion based on2-hydroxymethyltetrahydropyran fed) and 0.439 g of 16HD (6.2% molaryield based on 2-hydroxymethyltetrahydropyran fed).

After 65 days on stream the liquid feed was switched to a 4.7 wt %tetrahydrofuran-2,5-dimethanol in water solution with a flow rate of0.158 mL min⁻¹ at the same time the reactor temperature was lowered to240° C. After 66 days on stream a one hour averaged steady state samplewas collected. The 12.95 g sample solution contained 0.392 g oftetrahydrofuran-2,5-dimethanol (37.3% conversion based ontetrahydrofuran-2,5-dimethanol fed) and 0.019 g of 16HD (3.5% molaryield based on tetrahydrofuran-2,5-dimethanol fed).

Example 258 Conversion of 1,2,6-Hexanetriol to a Reaction MixtureComprising 1,6-Hexanediol in a Continuous Trickle Bed Reactor

This Example was carried out in a stainless steel (SS316) continuoustrickle bed reactor (ID=0.4 cm) using the following procedure.

The reactor was packed with approximately 1 mL of catalyst. If thecatalyst was not pre-reduced, the following procedure was used for insitu reduction: the reactor was heated at a rate of 1° C./min underforming gas (5% H₂ in N₂) to the desired reduction temperature (seeexamples), where it was held for the desired hold-up time, typically 2-3hours. The pre-reduced or in-situ reduced catalyst was used for runningmultiple reactions under varying reaction conditions (temperature,pressure, feed concentrations). The reactor temperature was adjusted tothe target first reaction condition temperature and held overnight underforming gas and either water or aqueous substrate solution. Subsequentlythe first reaction condition started by changing the gas feed to 100% H₂and the liquid feed to the desired aqueous substrate concentration. Theliquid volumetric feed rate was adjusted to correspond to a targetliquid hourly space velocity (LHSV), which was measured in units of mLliquid feed/mL catalyst/h. Unless otherwise specified, the ratio of thegas volumetric flowrate to the liquid volumetric flowrate as measured atambient conditions (gas to oil ratio, GTO) was adjusted to a value of4,000. Liquid effluent samples at each reaction condition were takenafter continuous operation for a minimum of 24 hours. The liquid sampleswere analyzed by quantitative GC analysis.

For Example 258, the continuous reactor was charged with a PtW/TiO₂catalyst having M1=Pt and M2=W such that the loading of Pt on TiO₂ was 4wt % and the loading of W was such that the metal molar ratio ofPt/W=1.0. The catalyst was made according to Catalyst Preparation MethodA. Aqueous solutions of 2.5 wt % 1,2,6-hexanetriol were used as theliquid feed. The liquid volumetric feed rate corresponded to a liquidhourly space velocity (LHSV) equal to 0.5 mL liquid feed/mL catalyst/h.Results at 200° C. are presented in Table 14.

TABLE 14 Results for Example 258 (200° C.) H₂ Mole Pressure ContentProduct Molar Yields (mole %) Conv. Balance GTO (bar) (%) 1H 1P THPM12HD 15HD 16HD 15PD 1B 12PD 126HT (%) (%) 100 69 20 4.40 2.41 3.80 12.712.09 18.76 3.93 0.00 1.20 30.89 69.10 83.30 100 69 50 3.27 1.00 2.378.64 2.76 20.07 3.20 0.00 0.00 50.20 49.80 93.36 100 69 100 2.65 0.581.71 6.28 3.90 31.19 2.50 0.00 0.00 41.13 58.87 92.95 1000 69 5 4.7610.84 2.54 5.90 0.49 3.40 1.42 5.46 3.70 1.54 98.46 47.46 1000 69 204.27 4.76 3.60 12.51 3.21 13.95 7.35 1.04 2.35 20.51 79.49 77.35 1000 6950 3.00 1.95 2.53 9.74 4.31 18.03 5.89 0.00 0.98 38.57 61.43 89.68 100069 100 2.37 1.00 1.95 8.45 5.04 20.95 4.69 0.00 0.49 41.90 58.10 89.69100 100 50 0.00 0.00 1.38 3.00 0.95 9.06 1.05 0.00 0.00 86.88 13.12105.44 100 100 100 0.52 0.00 1.49 3.00 1.96 18.94 1.08 0.00 0.00 72.8227.18 103.92 1000 100 100 0.00 0.00 0.95 1.59 1.32 5.08 4.16 0.00 0.0086.99 13.01 102.85 1000 100 50 0.00 0.00 1.62 2.18 1.18 3.23 5.80 0.000.00 84.92 15.08 102.15

Example 259 Conversion of 126HT to a Reaction Mixture Comprising 16HDUsing a PtW/TiO₂ Catalyst Under Recycle Conditions

A feed solution comprising 30 parts 126HT, 5 parts deionized water, and65 parts n-hexanol was placed into a calibrated vessel.

For the first pass of Example 259, a 20.0 mL aliquot containing a netamount of 5.84 g of 126HT (6.00 g of 97% purity material) wastransferred from the calibrated vessel into a stainless steel (SS316)pressure reactor equipped with a fritted sample line and a magnetic stirbar. Subsequently about 2.00 g of 4% PtW/TiO₂ catalyst (1:1 Pt:W onAerolyst 7708 TiO₂) was added to the pressure reactor, which was thensealed, connected to a high pressure gas manifold, and purged withnitrogen gas (1000 psi) three times. About 800 psi of hydrogen was thenadded, the reactor heated to 160° C., and then the pressure was adjustedwith hydrogen to about 1000 psi. The progress of the reaction wasmonitored by taking two 0.100 mL samples. After 10 h, the reactor wasallowed to cool to room temperature within 2 hours and depressurized.The reaction product solution was diluted with n-propanol and a knownamount of diethylene glycol diethyl ether as an internal standard andfiltered through a standard 5 micron disposable filter. The remainingcatalyst was washed with n-hexanol and returned to the reactor. About100 mg of fresh catalyst was added to compensate for physical losses. Asample of the filtrate was analyzed by GC and GC/MS.; results are givenin Table 15.

For the second pass of this Example, the reactor was recharged withfresh feed solution and the second pass was conducted as described abovefor the first pass.

For the third pass of this Example, the reactor was recharged with freshfeed solution and the third pass was conducted as described above forthe first pass.

For the fourth pass of this Example, the reactor was recharged withfresh feed solution and the fourth pass was started as described abovefor the first pass. GC analysis of a sample taken after a run time of 10h revealed lower conversion when compared to the average of the previouspasses. The reaction time was extended to 24 h at 160° C., followed byanother 24 h at 180° C., before the reactor was allowed to cool to roomtemperature and the filtering and analysis procedure described for thefirst pass was followed.

Results for the filtered reaction product from each pass are presentedin Table 15.

TABLE 15 Results for Reaction Product Solution Obtained for Each Pass ofExample 259 % % % % % Mass Molar Molar Molar Molar Molar balance ConvYield Yield Yield Yield Yield (molar (molar Pass 16HD THPM 12HD 15HD15PD %) %) 1 41 2 <1 5 0 87 71 2 51 3 <1 5 0 92 79 3 31 2 <1 3 0 85 60 480 12 <1 8 1 102 99

Example 260 Conversion of Tetrahydro-2,5-Furandimethanol to a ReactionMixture Comprising 1,6-Hexanediol in a Continuous Trickle Bed Reactor

This Example was carried out in a stainless steel (SS316) continuoustrickle bed reactor (ID=0.4 cm) using the following procedure.

The reactor was packed with approximately 1 mL of catalyst preparedusing catalyst synthesis method A. The catalyst was pre-reduced usingthe following procedure for in situ reduction: the reactor was heated ata rate of 1° C./min under forming gas (5% H₂ in N₂) to the 150°, whereit was held for 3 hours. The in-situ reduced catalyst was used forrunning multiple reactions under varying reaction conditions(temperature, pressure, feed concentrations). The reactor temperaturewas adjusted to the target first reaction condition temperature and heldovernight under forming gas and either water or aqueous substratesolution. Subsequently, the first reaction condition started by changingthe gas feed to 100% H₂ and the liquid feed to the desired aqueoussubstrate concentration. The liquid volumetric feed rate was adjusted tocorrespond to a target liquid hourly space velocity (LHSV), which wasmeasured in units of mL liquid feed/mL catalyst/h. Unless otherwisespecified, the ratio of the gas volumetric flowrate to the liquidvolumetric flowrate as measured at ambient conditions (gas to oil ratio,GTO) was adjusted to a value of 1,000. Liquid effluent samples at eachreaction condition were taken after continuous operation for a minimumof 24 hours. The liquid samples were analyzed by quantitative GCanalysis.

For Example 260, the continuous reactor was charged with a catalysthaving M1=Pt and M2=W such that the loading of Pt on ZrO₂(Saint-Gobain-NorPro SZ31107) was 4 wt % and the loading of W was suchthat the metal molar ratio of Pt/W=1.0; the catalyst was preparedaccording to Catalyst Preparation Method A. Aqueous solutions of 2.5 wt% THFdM were used as the liquid feed. The liquid volumetric feed ratecorresponded to a liquid hourly space velocity (LHSV) equal to 0.5 mLliquid feed/mL catalyst/h. In one condition, the catalyst was operatedat 100 bar and 140° C. At this condition, the observed conversion was 99mol % with a molar yield to 16HD of 59%.

Example 261 Conversion of 1,2,6-HT to a Reaction Mixture Comprising1,6-Hexanediol in a Continuous Trickle Bed Reactor

Example 261 was carried out as described for Example 281 except that asolution of 2.5 wt % 126HT with 5 wt % H₂O and the balance 1-hexanol wasused as the liquid feed, and the temperature was 120° C. At thiscondition, the observed conversion was 100 mol % with a molar yield to16HD of 71%.

Examples 262-269 Hydrodeoxygenation of THPM to 16HD Using a PhysicalMixture of M1M2/Support Catalyst and an Additive

These Examples were performed following the procedure of Examples 1-11except adding 50 mg of an additive as noted in Table 16, and using a140° C. temperature, an aqueous solution of 5 wt %2-hydroxymethyltetrahydropyran (THPM) as the substrate, and a PtW/SiO₂catalyst containing 4 wt % Pt and having Pt/W=1. The additive was notimpregnated with a metal. Results are presented in Table 16.

TABLE 16 Conversion of THPM to 16HD Using M1M2/Support Catalysts inCombination with an Additive at 1000 psig H₂. % Yield Catalyst % of Ex(M1M2/Support) Additive Conversion 16HD 262 PtW/SiO₂ None 13.1 1.5 263PtW/SiO₂ None 12.8 1.6 264 PtW/SiO₂ SiO2 13.6 2.9 265 PtW/SiO₂ SiO2 16.24.8 266 PtW/SiO₂ SiO2 14.5 3.3 267 PtW/SiO₂ TiO2 55.5 47.0 268 PtW/SiO₂TiO2 60.4 52.1 269 PtW/SiO₂ TiO2 60.2 50.6

The table above shows that, for a given M1M2/support catalyst, yield to16HD at a given temperature was increased when an additive was presentas a physical mixture with the catalyst. Compared to the Examples withPtW/SiO₂ alone and with extra non-impregnated SiO₂, PtW/SiO₂ is shown tohave increased yield to 1,6-HD with the addition of TiO₂ at 140° C.(Examples 267-269). Other combinations are possible and are not limitedto TiO₂.

Examples 270-273 Hydrodeoxygenation of THF-2-MeOH to 1,5-PentanediolUsing M1M2/Support Catalysts

Examples 270-273 were performed following the procedure of Examples 1-11except using the M1M2/support catalysts, a temperature of 140° C., andtetrahydrofurfuryl alcohol in place of 126HT. Results are shown in Table17.

TABLE 17 Results for Examples 270-273 Example M1M2/Support Catalyst %Yield of 15PD 270 PtW/TiO₂ 4% Pt; Pt/W = 1 56.1 271 IrRe/CBV780 4% Ir;Ir/Re = 1 52.1 272 IrRe/CBV780 4% Ir; Ir/Re = 1 45.0 273 RhRe/CBV780 4%Rh, Rh/Re = 1 15.8

Comparative Examples A-R

Comparative Examples A-R were performed following the procedure ofExamples 1-11 except using the catalysts and temperatures shown in Table18. The M1M2/support catalysts were prepared according to CatalystPreparation Method A. The M1/support catalysts were also preparedaccording to Catalyst Preparation Method A except that there was noaddition of a second metal. The results show that no 16HD was observedin the reaction solutions.

TABLE 18 Results for Comparative Examples A-R. Temp % % Yield of CompEx. (° C.) Catalyst Conv 16HD A 140 W/TiO₂ 4% W 0 0 B 140 W/TiO₂ 24% W 00 C 250 PdW/TiO₂ 4% Pd; Pd/W = 1 100 0 D 250 IrRe/CBV780 4% Ir; Re/Ir =1 100 0 E 180 RhMo/TiO₂ 4% Rh; Rh/Mo = 1 100 0 F 180 IrRe/CBV780 4% Ir;Ir/Re = 1 100 0 G 180 IrRe/TiO₂ 4% Ir; Ir/Re - 1:1 100 0 H 250 RhMo/TiO₂4% Rh; Rh/Mo = 1 100 0 J 250 RhZr/Celite 4% Rh; Rh/Zr = 2 100 0 K 180Fe/WO₃ 10% Fe 0 0 L 140 WOx 0 0 M 140 Pt/SiO₂ 4% Pt 0 0 N 140 Pt/Al₂O₃4% Pt 0 0 P 140 W/Al₂O₃ 4% W 0 0 Q 140 PtW/MgO 4% Pt Pt/W = 1 0.5 0 R140 PtW/NbO 4% Pt Pt/W = 1 0 0

Comparative Examples S, T, and V

Comparative Examples S, T, and V were performed following the procedureof Examples 83-190 except using 180° C., the catalysts shown in Table19, and 2-hydroxymethyltetrahydropyran as the substrate instead of126HT. The catalysts used in these Comparative Examples contained 4weight percent Pt and were prepared according to Catalyst PreparationMethod A except that there was no addition of a second metal. Theresults show that no 16HD was observed in the reaction solutions forComparative Examples S and T, and selectivity to 16HD was very low forComparative Example V.

TABLE 19 Results for Comparative Examples S-V. Comp Catalyst % sel to %sel to % sel to Ex (M1/Support) % Conv 1P 1H 16HD S Pt/Al₂O₃ 2.94 1.5311.65 0 T Pt/SiO₂ 2.23 1.46 11.19 0 V Pt/CBV780 2.65 1.49 11.08 1.4

1. A process for preparing an α,ω-C_(n)-diol, comprising the steps: (a)providing a feedstock comprising a C_(n) oxygenate; (b) contacting thefeedstock with hydrogen gas, in the presence of a catalyst at atemperature and for a time sufficient to form a product mixturecomprising an α,ω-C_(n)-diol; wherein n is 5 or greater; and wherein thecatalyst comprises a metal M1 and a metal M2 or an oxide of M2, andoptionally a support, wherein: M1 is Rh and M2 is Mo, W, V, Mn, Ni, Cu,Zn, Cr, Ge, Sn, Ti, Au, or Zr; or M1 is Ag, Au or Co; and M2 is Re, Mo,or W; or M1 is Cu, Fe, or Ni; and M2 is Re, Mo, Zn, Cr, Ge, Sn, or W; orM1 is Co and M2 is Fe; or M1 is Ni and M2 is Co or Fe; or M1 is Mn andM2 is Cr.
 2. The process of claim 1, wherein n=5 or
 6. 3. The process ofclaim 1 wherein the optional support is present in the catalyst andcomprises WO₃, SiO₂, Al₂O₃, carbon, TiO₂, ZrO₂, SiO₂—Al₂O₃,montmorillonite, SiO₂—TiO₂, tungstated ZrO₂, zeolites, V₂O₅, MoO₃, ormixtures thereof.
 4. The process of claim 1 wherein the C_(n) oxygenatecomprises 1,2,6-hexanetriol; 1,2,5-pentanetriol;2H-tetrahydropyran-2-methanol; tetrahydrofuran-2,5-dimethanol;furan-2,5-dimethanol; 2,5 dihydrofuran-2,5-dimethanol; levoglucosenone;levoglucosan; levoglucosenol;1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one; isosorbide;hydroxymethylfurfural; sorbitol; glucose; fructose; xylitol;3,4-dihydro-2H-pyran-2-carbaldehyde; 1,2,5,6-hexanetetraol;1,2,3,5,6-hexanepentanol; 1,5-anhydro-3,4-dideoxy-hexitol;5-hydroxy-2H-tetrahydropyran-2 methanol; furfural; furfuryl alcohol;tetrahydrofurfuryl alcohol; pentoses; dimers containing pentose;oligomers containing pentose; hexoses; dimers containing hexose;oligomers containing hexose; condensation products from the reaction of5-(hydroxymethyl)-2-furfural (“HMF”) with ketones and/or aldehydes, andcondensation products from the reaction of furfural with ketones and/oraldehydes.
 5. The process of claim 4, wherein the C_(n) oxygenatecomprises 1,2,6-hexanetriol; 2H-tetrahydropyran-2-methanol;tetrahydrofuran-2,5-dimethanol; levoglucosenone;3,4-dihydro-2H-pyran-2-carbaldehyde, or mixtures thereof.
 6. The processof claim 5, wherein the C_(n) oxygenate comprises 1,2,6-hexanetriol. 7.The process of claim 4, wherein the C_(n) oxygenate comprises1,2,5-pentanetriol; furfural; furfuryl alcohol; tetrahydrofurfurylalcohol; xylitol; or mixtures thereof.
 8. (canceled)
 9. (canceled) 10.(canceled)
 11. (canceled)
 12. (canceled)
 13. (canceled)
 14. The processof claim 1, further comprising the steps: (c) optionally, isolating theα,ω-C_(n)-diol from the product mixture; (d) contacting theα,ω-C_(n)-diol with ammonia and hydrogen in the presence of a reductiveamination catalyst at a temperature and for a time sufficient to form asecond product mixture comprising an α,ω-C_(n)-diaminoalkane; and (e)optionally, isolating the α,ω-C_(n)-diaminoalkane from the secondproduct mixture.
 15. The process of claim 14, wherein theα,ω-C_(n)-diaminoalkane comprises 1,6-diaminohexane.
 16. (canceled) 17.(canceled)
 18. The process of claim 15 wherein the C_(n) oxygenatecomprises 1,2,6-hexanetriol; 1,2,5-pentanetriol;2H-tetrahydropyran-2-methanol; tetrahydrofuran-2,5-dimethanol;furan-2,5-dimethanol; 2,5 dihydrofuran-2,5-dimethanol; levoglucosenone;levoglucosan; levoglucosenol;1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one; isosorbide;hydroxymethylfurfural; sorbitol; glucose; fructose; xylitol;3,4-dihydro-2H-pyran-2-carbaldehyde; 1,2,5,6-hexanetetraol;1,2,3,5,6-hexanepentanol; 1,5-anhydro-3,4-dideoxy-hexitol;5-hydroxy-2H-tetrahydropyran-2 methanol; furfural; furfuryl alcohol;tetrahydrofurfuryl alcohol; pentoses; dimers containing pentose;oligomers containing pentose; hexoses; dimers containing hexose;oligomers containing hexose; condensation products from the reaction of5-(hydroxymethyl)-2-furfural (“HMF”) with ketones and/or aldehydes, andcondensation products from the reaction of furfural with ketones and/oraldehydes.
 19. (canceled)
 20. (canceled)